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
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
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
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
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
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
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
Lithium-aluminum layered double hydroxides(LiAl-LDH)have been be successfully applied in commercial-scale for lithium extraction from salt lake brine,however,further advancement of their applications is hampered by su...Lithium-aluminum layered double hydroxides(LiAl-LDH)have been be successfully applied in commercial-scale for lithium extraction from salt lake brine,however,further advancement of their applications is hampered by suboptimal Li^(+)adsorption performance and ambiguous extraction process.Herein,a doping engineering strategy was developed to fabricate novel Zn^(2+)-doped LiAl-LDH(LiZnAl-LDH)with remarkable higher Li^(+)adsorption capacity(13.4 mg/g)and selectivity(separation factors of 213,834,171 for Li^(+)/K^(+),Li^(+)/Na^(+),Li^(+)/Mg^(2+),respectively),as well as lossless reusability in Luobupo brine compared to the pristine LiAl-LDH.Further,combining experiments and simulation calculations,it was revealed that the specific surface area,hydrophilic,and surface attraction for Li^(+)of LiZnAl-LDH were significantly improved,reducing the adsorption energy(Ead)and Gibbs free energy(ΔG),thus facilitating the transfer of Li^(+)from brine into interface followed by insertion into voids.Importantly,the intrinsic oxygen vacancies derived from Zn-doping depressed the diffusion energy barrier of Li^(+),which accelerated the diffusion process of Li^(+)in the internal bulk of LiZnAl-LDH.This work provides a general strategy to overcome the existing limitations of Li^(+)recovery and deepens the understanding of Li^(+)extraction on LiAl-LDH.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
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
Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological...Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological alternative is the electrochemical oxidation of the cathode materials,whereby lithium can be deintercalated and transferred to an electrolyte solution without the aid of chemical extracting compounds.This article investigates the potential to selectively recover Li from LIB cathode materials by direct electrochemical extraction in aqueous solutions.The process allowed to recovering up to 98%of Li from high-purity commercial cathode materials(LiMn_(2)O_(4),LiCoO_(2),and Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2))with a faradaic efficiency of 98%and negligible co-extraction of Co,Ni,and Mn.The process was then applied to recover Li from the real waste LIBs black mass obtained by the physical treatment of electric vehicle battery packs.This black mass contained graphite,conductive carbon,and metal impurities from current collectors and steel cases,which significantly influenced the evolution and performances of Li electrochemical extraction.Particularly,due to concomitant oxidation of impurities,lithium extraction yields and faradaic efficiencies were lower than those obtained with high-purity cathode materials.Copper oxidation was found to occur within the voltage range investigated,but it could not quantitatively explain the reduced Li extraction performances.In fact,a detailed investigation revealed that above 1.3 V vs.Ag/Ag Cl,conductive carbon can be oxidized,contributing to the decreased Li extraction.Based on the reported experimental results,guidelines were provided that quantitatively enable the extraction of Li from the black mass,while preventing the simultaneous oxidation of impurities and,consequently,reducing the energy consumption of the proposed Li recovery method.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
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
Lepidolites are important carriers of Li ores.Because of the strong positive correlation between the presence of Li and F,Li extracted from lepidolite must be defluorinated.Moreover,synergistically extracting Li,Rb,an...Lepidolites are important carriers of Li ores.Because of the strong positive correlation between the presence of Li and F,Li extracted from lepidolite must be defluorinated.Moreover,synergistically extracting Li,Rb,and Cs is important for the comprehensive utilization of lepidolite.Steam roasting converts F to HF without introducing impurities.In this study,the effects of steam roasting on Li activation and the synergistic extraction of Rb and Cs were investigated during the defluorination process.Notably,the defluorination mechanism and migration behavior of F during steam roasting were revealed based on qualitative and quantitative analyses of the liquid and corresponding solid phases.Furthermore,density functional theory calculations were used to investigate the pathways and behaviors of defluorination and the removal behavior of F atoms connected to Al and Li sites,revealing that the F atoms on the(010)crystal surface were easily replaced by water molecules,thereby releasing surface F atoms.Under the optimal roasting conditions,the defluorination efficiency of lepidolite was 91.08%at 880℃for 1 h.Subsequently,the Li encapsulated in the crystal lattice,as well as Rb and Cs,was activated and leached using optimal sulfuric acid leaching.The leaching efficiencies of Li,Rb,and Cs were 97.37%,97.77%,and 97.19%,respectively at 120℃for 2 h.This study provides a comprehensive and systematic perspective on the defluorination and comprehensive utilization of lepidolite,providing a comprehensive,clean,efficient,green,and low-C lepidolite Li extraction process.展开更多
The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluori...The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluorine-based chemical method, was carried out under crucial factors such as different HF/ore ratios(1:1-3:1 g/mL) and leaching temperatures(50-85℃). The kinetics data fit well with the developed shrinking-core model, indicating that the leaching rate of Li was controlled by the chemical reaction and inner diffusion at the beginning of leaching(0-30 min) as a calculated apparent activation energy(Ea) of 20.62 kJ/mol. The inner diffusion became the rate-limiting step as the leaching continues(60-180 min). Moreover, effects of HF/ore ratio and leaching temperature on selective leaching behavior of Li, Al and Si were discussed. 90% of fluorine mainly existed as HF/F-in leaching solution, which can provide theoretical guidance for further removal or recovery of F.展开更多
An enhanced leaching of Li fromα-spodumene was carried out using a mixture of hydrofluoric and sulfuric acid(HF/H_(2)SO_(4))as the medium.Based on the optimized leaching conditions,the leaching kinetics of Li was inv...An enhanced leaching of Li fromα-spodumene was carried out using a mixture of hydrofluoric and sulfuric acid(HF/H_(2)SO_(4))as the medium.Based on the optimized leaching conditions,the leaching kinetics of Li was investigated in an ore/HF/H_(2)SO_(4) ratio of 1:3:2 g:mL:mL with leaching temperature ranging from 50 to 100°C.The results indicate that the leaching kinetics of Li fitted well with a model based on the shrinking core model.In addition,the leaching rate of Li was controlled by chemical reactions and diffusion through the product layers.The apparent activation energy Ea was calculated to be 32.68 kJ/mol.Solid films were formed because of the generation of insoluble products such as cryolithionite(Na_(3)Li_(2)Al2F _(12) ),cryolite(Na_(3)AlF_(6)),calcium fluoride(CaF_(2)),potassium cryolite(K_(2)AlF_(5)),aluminum fluoride(AlF_(3)),and fluorosilicates(Na_(2)SiF_(6 )or KNaSiF_(6)).Furthermore,the effects of the ore/HF ratio and leaching temperature on the leaching behavior of Li,Al and Si were investigated.The results indicate that the ore/HF ratio and leaching temperature could clearly affect the distribution of HF molecules on the leaching of Li,Al and Si,which are important for the selective leaching of Li over Al and Si with this fluorine-based chemical method.展开更多
An acidic mixture of sulfuric and fluosilicic acid(H_(2)SO_(4)+H_(2)SiF_(6))was employed as lixiviant to enhance leaching of lithium from lepidolite.The H_(2)SiF_(6) was obtained as a byproduct of anhydrous hydrofluor...An acidic mixture of sulfuric and fluosilicic acid(H_(2)SO_(4)+H_(2)SiF_(6))was employed as lixiviant to enhance leaching of lithium from lepidolite.The H_(2)SiF_(6) was obtained as a byproduct of anhydrous hydrofluoric acid production,aiming to provide HF molecules.It was found that the HF molecules were the main reaction component and played a key role in strengthening the dissolution of lepidolite.Different factors,including mass ratio of ore/H_(2)SO_(4)/H_(2)SiF_(6),concentrations of H_(2)SO_(4) and H_(2)SiF_(6),leaching temperatures(40−80℃)and time(15−75 min),were investigated.Moreover,an efficient tubular reactor was employed to improve this acid leaching system.Under the optimal conditions(ore/H_(2)SO_(4)/H_(2)SiF_(6) mass ratio of 1:0.8:1.6,80 wt.% H_(2)SO_(4),15 wt.% H_(2)SiF_(6),80℃,15 min),97.9% of Li,96.4% of K,97.6% of Rb,96.7% of Cs and 81.4% of Al(mass fraction)were leached.Additionally,a two-step thermal process was proposed to remove fluorine of leaching slurry.This acid treatment using an acidic mixture of H_(2)SO_(4) and H_(2)SiF_(6) in a continuous tubular reactor shows potential as an alternative process to extract lithium from lepidolite.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
Development of high-performance ion-selective membranes is crucial for achieving efficient ion separation in water treatment and energy storage applications.In this study,we demonstrate the strategic incorporation of ...Development of high-performance ion-selective membranes is crucial for achieving efficient ion separation in water treatment and energy storage applications.In this study,we demonstrate the strategic incorporation of acid-base pairs within a polybenzimidazole matrix through controlled sulfonation.By leveraging these intermolecular interactions,we enhance the Li^(+)/Mg^(2+)selectivity of the membrane.At an optimal sulfonation degree,the SP45 membrane forms a cross-linked structure,featuring contracted ionic clusters and discrete hydrophilic domains with limited interconnectivity.This unique microstructure imposes significantly higher energy barriers for the transmembrane transport of Mg^(2+),thereby endowing the SP45 membrane with exceptional perm-selectivity of 48.1 at a current density of 2 mA cm^(-2).Cycling stability tests reveal that the Li^(+)/Mg^(2+)selectivity degradation remains below 10%across multiple cycles in diverse mixed-salt systems.In practical brine ion distillation tests,we achieved a separation factor of exceeding 60,000 between Li^(+)and Mg^(2+)utilizing a 4-stage ion-distillation device equipped with the prepared SP45 membranes.This work provides fundamental insights into ion transport regulation through molecular-level acid-base pairs engineering,opening new avenues for advanced ion-selective separation membranes.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.
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supports for this work from National Key R&D Program of China(No.2022YFC2906300)the National Natural Science Foundation of China(No.52204283)+2 种基金the Natural Science Foundation of Hubei Province of China(No.2021CFB554)the Key Project of the Science and Technology Research of Hubei Provincial Department of Education(No.D20221605)the CONACYT through the project A1-S-8817.L.J.Z.would like to thank CONACYT for the scholarship for granting his the scholarship No.847199 during his Ph.D study.
文摘Lithium-aluminum layered double hydroxides(LiAl-LDH)have been be successfully applied in commercial-scale for lithium extraction from salt lake brine,however,further advancement of their applications is hampered by suboptimal Li^(+)adsorption performance and ambiguous extraction process.Herein,a doping engineering strategy was developed to fabricate novel Zn^(2+)-doped LiAl-LDH(LiZnAl-LDH)with remarkable higher Li^(+)adsorption capacity(13.4 mg/g)and selectivity(separation factors of 213,834,171 for Li^(+)/K^(+),Li^(+)/Na^(+),Li^(+)/Mg^(2+),respectively),as well as lossless reusability in Luobupo brine compared to the pristine LiAl-LDH.Further,combining experiments and simulation calculations,it was revealed that the specific surface area,hydrophilic,and surface attraction for Li^(+)of LiZnAl-LDH were significantly improved,reducing the adsorption energy(Ead)and Gibbs free energy(ΔG),thus facilitating the transfer of Li^(+)from brine into interface followed by insertion into voids.Importantly,the intrinsic oxygen vacancies derived from Zn-doping depressed the diffusion energy barrier of Li^(+),which accelerated the diffusion process of Li^(+)in the internal bulk of LiZnAl-LDH.This work provides a general strategy to overcome the existing limitations of Li^(+)recovery and deepens the understanding of Li^(+)extraction on LiAl-LDH.
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the Horizon Europe Project“Batteries reuse and direct production of high performances cathodic and anodic materials and other raw materials from batteries recycling using low cost and environmentally friendly technologies” (RHINOCEROS project,grant no.101069685)。
文摘Lithium recovery from end-of-life Li-ion batteries(LIBs)through pyro-and hydrometallurgical recycling processes involves several refining stages,with high consumption of reagents and energy.A competitive technological alternative is the electrochemical oxidation of the cathode materials,whereby lithium can be deintercalated and transferred to an electrolyte solution without the aid of chemical extracting compounds.This article investigates the potential to selectively recover Li from LIB cathode materials by direct electrochemical extraction in aqueous solutions.The process allowed to recovering up to 98%of Li from high-purity commercial cathode materials(LiMn_(2)O_(4),LiCoO_(2),and Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2))with a faradaic efficiency of 98%and negligible co-extraction of Co,Ni,and Mn.The process was then applied to recover Li from the real waste LIBs black mass obtained by the physical treatment of electric vehicle battery packs.This black mass contained graphite,conductive carbon,and metal impurities from current collectors and steel cases,which significantly influenced the evolution and performances of Li electrochemical extraction.Particularly,due to concomitant oxidation of impurities,lithium extraction yields and faradaic efficiencies were lower than those obtained with high-purity cathode materials.Copper oxidation was found to occur within the voltage range investigated,but it could not quantitatively explain the reduced Li extraction performances.In fact,a detailed investigation revealed that above 1.3 V vs.Ag/Ag Cl,conductive carbon can be oxidized,contributing to the decreased Li extraction.Based on the reported experimental results,guidelines were provided that quantitatively enable the extraction of Li from the black mass,while preventing the simultaneous oxidation of impurities and,consequently,reducing the energy consumption of the proposed Li recovery method.
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.
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Thermodynamic calculation of defluorination process using the HSC Chemistry 10 was supported by Prof.Huan Li,from the Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences(CAS)The financial support from the National Natural Science Foundation of China(No.52104271)+2 种基金Natural Science Foundation of Henan,China(No.242300421222)the Open Project Program of Key Laboratory of Metallurgical Emission Reduction & Resources Recycling(Anhui University of Technology),Ministry of Education(No.JKF24-02)the Project of Zhongyuan Critical Metals Laboratory(No.GJJSGFYQ202416)were greatly acknowledged
文摘Lepidolites are important carriers of Li ores.Because of the strong positive correlation between the presence of Li and F,Li extracted from lepidolite must be defluorinated.Moreover,synergistically extracting Li,Rb,and Cs is important for the comprehensive utilization of lepidolite.Steam roasting converts F to HF without introducing impurities.In this study,the effects of steam roasting on Li activation and the synergistic extraction of Rb and Cs were investigated during the defluorination process.Notably,the defluorination mechanism and migration behavior of F during steam roasting were revealed based on qualitative and quantitative analyses of the liquid and corresponding solid phases.Furthermore,density functional theory calculations were used to investigate the pathways and behaviors of defluorination and the removal behavior of F atoms connected to Al and Li sites,revealing that the F atoms on the(010)crystal surface were easily replaced by water molecules,thereby releasing surface F atoms.Under the optimal roasting conditions,the defluorination efficiency of lepidolite was 91.08%at 880℃for 1 h.Subsequently,the Li encapsulated in the crystal lattice,as well as Rb and Cs,was activated and leached using optimal sulfuric acid leaching.The leaching efficiencies of Li,Rb,and Cs were 97.37%,97.77%,and 97.19%,respectively at 120℃for 2 h.This study provides a comprehensive and systematic perspective on the defluorination and comprehensive utilization of lepidolite,providing a comprehensive,clean,efficient,green,and low-C lepidolite Li extraction process.
基金Project(51474237)supported by the National Natural Science Foundation of China
文摘The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluorine-based chemical method, was carried out under crucial factors such as different HF/ore ratios(1:1-3:1 g/mL) and leaching temperatures(50-85℃). The kinetics data fit well with the developed shrinking-core model, indicating that the leaching rate of Li was controlled by the chemical reaction and inner diffusion at the beginning of leaching(0-30 min) as a calculated apparent activation energy(Ea) of 20.62 kJ/mol. The inner diffusion became the rate-limiting step as the leaching continues(60-180 min). Moreover, effects of HF/ore ratio and leaching temperature on selective leaching behavior of Li, Al and Si were discussed. 90% of fluorine mainly existed as HF/F-in leaching solution, which can provide theoretical guidance for further removal or recovery of F.
基金Project(51474237) supported by the National Natural Science Foundation of China
文摘An enhanced leaching of Li fromα-spodumene was carried out using a mixture of hydrofluoric and sulfuric acid(HF/H_(2)SO_(4))as the medium.Based on the optimized leaching conditions,the leaching kinetics of Li was investigated in an ore/HF/H_(2)SO_(4) ratio of 1:3:2 g:mL:mL with leaching temperature ranging from 50 to 100°C.The results indicate that the leaching kinetics of Li fitted well with a model based on the shrinking core model.In addition,the leaching rate of Li was controlled by chemical reactions and diffusion through the product layers.The apparent activation energy Ea was calculated to be 32.68 kJ/mol.Solid films were formed because of the generation of insoluble products such as cryolithionite(Na_(3)Li_(2)Al2F _(12) ),cryolite(Na_(3)AlF_(6)),calcium fluoride(CaF_(2)),potassium cryolite(K_(2)AlF_(5)),aluminum fluoride(AlF_(3)),and fluorosilicates(Na_(2)SiF_(6 )or KNaSiF_(6)).Furthermore,the effects of the ore/HF ratio and leaching temperature on the leaching behavior of Li,Al and Si were investigated.The results indicate that the ore/HF ratio and leaching temperature could clearly affect the distribution of HF molecules on the leaching of Li,Al and Si,which are important for the selective leaching of Li over Al and Si with this fluorine-based chemical method.
基金the financial supports from Natural Science Foundation of Henan,China(No.212300410278)Henan Provincial Key Research and Development Program,China(No.212102310371)+1 种基金Henan Postdoctoral Foundation,China(No.202002020)China Postdoctoral Science Foundation(No.2020M682353).
文摘An acidic mixture of sulfuric and fluosilicic acid(H_(2)SO_(4)+H_(2)SiF_(6))was employed as lixiviant to enhance leaching of lithium from lepidolite.The H_(2)SiF_(6) was obtained as a byproduct of anhydrous hydrofluoric acid production,aiming to provide HF molecules.It was found that the HF molecules were the main reaction component and played a key role in strengthening the dissolution of lepidolite.Different factors,including mass ratio of ore/H_(2)SO_(4)/H_(2)SiF_(6),concentrations of H_(2)SO_(4) and H_(2)SiF_(6),leaching temperatures(40−80℃)and time(15−75 min),were investigated.Moreover,an efficient tubular reactor was employed to improve this acid leaching system.Under the optimal conditions(ore/H_(2)SO_(4)/H_(2)SiF_(6) mass ratio of 1:0.8:1.6,80 wt.% H_(2)SO_(4),15 wt.% H_(2)SiF_(6),80℃,15 min),97.9% of Li,96.4% of K,97.6% of Rb,96.7% of Cs and 81.4% of Al(mass fraction)were leached.Additionally,a two-step thermal process was proposed to remove fluorine of leaching slurry.This acid treatment using an acidic mixture of H_(2)SO_(4) and H_(2)SiF_(6) in a continuous tubular reactor shows potential as an alternative process to extract lithium from lepidolite.
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supported by the National Key Research and Development Program of China(2022YFB3805100)National Natural Science Foundation of China(22222812 and 22178330).
文摘Development of high-performance ion-selective membranes is crucial for achieving efficient ion separation in water treatment and energy storage applications.In this study,we demonstrate the strategic incorporation of acid-base pairs within a polybenzimidazole matrix through controlled sulfonation.By leveraging these intermolecular interactions,we enhance the Li^(+)/Mg^(2+)selectivity of the membrane.At an optimal sulfonation degree,the SP45 membrane forms a cross-linked structure,featuring contracted ionic clusters and discrete hydrophilic domains with limited interconnectivity.This unique microstructure imposes significantly higher energy barriers for the transmembrane transport of Mg^(2+),thereby endowing the SP45 membrane with exceptional perm-selectivity of 48.1 at a current density of 2 mA cm^(-2).Cycling stability tests reveal that the Li^(+)/Mg^(2+)selectivity degradation remains below 10%across multiple cycles in diverse mixed-salt systems.In practical brine ion distillation tests,we achieved a separation factor of exceeding 60,000 between Li^(+)and Mg^(2+)utilizing a 4-stage ion-distillation device equipped with the prepared SP45 membranes.This work provides fundamental insights into ion transport regulation through molecular-level acid-base pairs engineering,opening new avenues for advanced ion-selective separation membranes.
