To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.He...To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.Here,we report a low-potential photoelectrochemical(PEC)system that selectively and efficiently extracts Li metals from multi-cation electrolytes under 1 sun illumination.Based on the difference of redox potential,we can get rid of the disturbance of other cations(i.e.,Fe,Co and Ni ions)by a bias-free PEC device to realize the extraction of high-purity Li metals on a coplanar Si-based photocathode-TiO_(2) photoanode tandem device at 2 V of applied bias(far less than the redox potentials of Li^(+)/Li).In such system,the extraction rate of Li metals(purity>99.5%)exceeds 1.35 g h^(-1)m^(-2)with 90%of Faradaic efficiency.Long-term experiments,different electrode/electrolyte tests,and various price assessments further demonstrate the stability,compatibility and economy of PEC extraction system,enabling a solar-driven pathway for the recycling of critical metal resources.展开更多
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
Developing selective electrodes for lithium extraction from brines remains challenging.This work reports room-temperature synthesized cubic copper hexacyanoferrate(Cu HCF)nanoparticles for hybrid capacitive deionizati...Developing selective electrodes for lithium extraction from brines remains challenging.This work reports room-temperature synthesized cubic copper hexacyanoferrate(Cu HCF)nanoparticles for hybrid capacitive deionization(HCDI).The Cu HCF framework exhibits a high surface area(715.84 m^(2)·g^(-1)),dual redoxactive sites([Fe^(Ⅲ)(CN)_(6)]^(4-)/[Fe^(Ⅱ)(CN)_(6)]^(3-)and Cu^(+)/Cu^(2+)),and excellent cyclability(99.4%capacity retention after 1000 cycles).In HCDI system,the Cu HCF cathode demonstrates remarkable Li^(+)ions selectivity,achieving a 25.5 mg·g^(-1)adsorption capacity in 500 mg·L^(-1)Li Cl solution with 94%charge efficiency at1.2 V.Notably,in mixed Li^(+)/Mg^(2+)solutions(30:1 molar ratio),Cu HCF nanoparticles maintain a high separation coefficient of 3.1,attributed to the synergistic effects of ionic sieving and preferential redox interactions.Mechanistic studies confirm Li^(+)(de)intercalation via reversible[Fe^(Ⅲ)(CN)_(6)]^(4-)/[Fe^(Ⅱ)(CN)_(6)]^(3-)and Cu^(2+)/Cu^(+)transitions.Density functional theory calculations reveal Li^(+)exhibits lower adsorption energy than Mg^(2+)(-3.72 e V vs.-1.49 e V),which fundamentally explains the preferential extraction capability of Li^(+)ions over Mg^(2+)ions during the separation process.This study advances ion-selective pseudocapacitor design for sustainable lithium extraction from high-salinity resources.展开更多
Lithium-ion batteries(LIBs)that reached their end-of-life(EoL)require recycling,rather than disposal,to recirculate valuable metals and protect the environment.This led us to investigate the extraction of metals from ...Lithium-ion batteries(LIBs)that reached their end-of-life(EoL)require recycling,rather than disposal,to recirculate valuable metals and protect the environment.This led us to investigate the extraction of metals from the cathodes of EoL lithium-titanate batteries using ethylenediaminetetraacetic acid disodium(EDTA-2Na).In this work,an orthogonal array was used to design experiments and sig-nal-to-noise calculations were used to define the optimal conditions,which were 0.50 mol/L EDTA-2Na,pH=6,75℃,180 min,2%pulp density,and 300 r/min,resulting in 97.96%,94.79%,96.45%,and 98.89%leaching efficiencies for Li,Ni,Co,and Mn,respectively.Stat-istically significant interactions between variables were then identified using Pearson’s correlation at the 95%confidence interval,and the pH and temperature were found to be significant.The extraction efficiency decreased as the pH increased,but increased as the temperat-ure increased.Machine learning fitting using linear regression for multi-output prediction was unsatisfactory,whereas random forest re-gression(RFR)produced satisfactory results.Permutation importance was computed on the fitted RFR to determine feature importance,and confirmed that the pH and temperature were influential variables;however,the time and pulp density were also noted.As the fitted RFR failed to satisfactorily predict leaching efficiencies in additional validation experiments,we recommend increasing the number of ex-periments and using additional fitting models.An additional analysis that included the initial oxidation-reduction potential(optimal 33.3 mV)revealed this to be the most important variable,the effect of which largely overshadows those of all the other variables.Finally,an environmental assessment highlighted the benefits of the chelating extraction;however,the economic assessment indicated room for improvement.展开更多
An inverse spinel-type metal oxide, magnesium-manganese-titanium oxide （Mg2Mn0.5Ti0.5O4）, were prepared using the coprecipitation/thermal crystallization method. The extraction/insertion reaction with this material ...An inverse spinel-type metal oxide, magnesium-manganese-titanium oxide （Mg2Mn0.5Ti0.5O4）, were prepared using the coprecipitation/thermal crystallization method. The extraction/insertion reaction with this material was investigated by X-ray, saturation capacity of exchange, pH titration, and distribution coefficient （Kd） measurement. The acid treatments of Mg2Mn0.5Ti0.5O4 caused Mg^2＋ extractions of more than 81%, whereas the dissolutions of Mn^4＋ and Ti^4＋ were less than 10%. The experimental results proved that the acid-treated sample has a capacity of exchange 56 mg·g^-1 for Li^＋ in the solution. The chemical analysis showed that the Li^＋ extraction/insertion progressed mainly by ion-exchange mechanism and surface adsorption.展开更多
Rechargeable aqueous zinc ion batteries(AZIBs)were considered as one of the most promising candidates for large-scale energy storage due to the merits of high safety and inexpensiveness.As AZIBs cathode material,Mn O_...Rechargeable aqueous zinc ion batteries(AZIBs)were considered as one of the most promising candidates for large-scale energy storage due to the merits of high safety and inexpensiveness.As AZIBs cathode material,Mn O_(2)possesses great merits but was greatly hindered due to the sluggish diffusion kinetic of Zn^(2+) during electrochemical operations.Herein,deep Zn^(2+) ions intercalatedδ-Mn O_(2)(Zn-Mn O_(2))was achieved by the in situ electrochemical deposition route,which significantly enhanced the diffusion ability of Zn^(2+) due to the synergistic effects of Zn^(2+) pillars and structural H;O.The resultant Zn-Mn O_(2)based AZIBs delivers a record capacity of 696 m Ah/g(0.5 m Ah/cm^(2))based on the initial mass loading,which is approaching the theoretical capacity of Mn O_(2)with a two-electrons reaction.In-situ Raman studies reveal highly reversible Zn^(2+)ions insertion/extraction behaviors and here the Zn-Mn O_(2)plays the role of a container during the charge–discharge process.Further charge storage mechanism investigations point out the insertion/extraction of Zn^(2+) and H^(+) coincides,and such process is significantly facilitated results from superior interlayered configurations of Zn-Mn O_(2)The excellent electrochemical performance of Zn-Mn O_(2)achieved in this work suggests the deep ions pre-intercalation strategy may aid in the future development of advanced cathodes for AZIBs.展开更多
Electrochemical insertion/extraction of Li on cathode materials of spinel type LiMn2O4 and ordered rock-salt type LiCo0.5 Ni0.5O2 was measured on samples of which structures were well characterized. On the basis of ex...Electrochemical insertion/extraction of Li on cathode materials of spinel type LiMn2O4 and ordered rock-salt type LiCo0.5 Ni0.5O2 was measured on samples of which structures were well characterized. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materiaIs on electrochemical Li insertion/extraction performance was discussed. These two transition metal oxides belong to onegroup that the crystallinity of these oxides affects to the performance.展开更多
Electrochemical insertion/extraction of Li on cathode materials of anatase type TiO_2, quasilayered structure V_2O_5 and layered structure MoO_3 was measured on samples of which structures were well characterized and...Electrochemical insertion/extraction of Li on cathode materials of anatase type TiO_2, quasilayered structure V_2O_5 and layered structure MoO_3 was measured on samples of which structures were well characterized and showed a wide range of crystallinity. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materials on electrochemical Li insertion/extraction pedermance was discussed. These three transition metal oxides were classified as one group on the basis of whether the crystallinity of these oxides affects to the performance or not; LiMn_2O_4 and LiCo_(0.5)O_2 belongs to the former group and TiO_2, V_2O_5 and MoO_3 to the latter.展开更多
The work distills the main mechanisms during the lithium insertion/extraction of LiFePO_4 cathode materials. The "diffusion-controlled" and "phase-boundary controlled" mechanism are especially illu...The work distills the main mechanisms during the lithium insertion/extraction of LiFePO_4 cathode materials. The "diffusion-controlled" and "phase-boundary controlled" mechanism are especially illustrated. Meanwhile, some recent observation and analyses by in-situ or in operando on the Li-insertion/extraction of LiFePO_4 are summarized and prospected.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
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
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
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
Lithium is considered to be the most important energy metal of the 21st century.Because of the development trend of global electrification,the consumption of lithium has increased significantly over the last decade,an...Lithium is considered to be the most important energy metal of the 21st century.Because of the development trend of global electrification,the consumption of lithium has increased significantly over the last decade,and it is foreseeable that its demand will continue to increase for a long time.Limited by the total amount of lithium on the market,lithium extraction from natural resources is still the first choice for the rapid development of emerging industries.This paper reviews the recent technological developments in the extraction of lithium from natural resources.Existing methods are summarized by the main resources,such as spodumene,lepidolite,and brine.The advantages and disadvantages of each method are compared.Finally,reasonable suggestions are proposed for the development of lithium extraction from natural resources based on the understanding of existing methods.This review provides a reference for the research,development,optimization,and industrial application of future processes.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
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
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
基金the National Natural Science Foundation of China(22479047,22409058)the Outstanding Youth Scientist Foundation of Hunan Province(2022JJ10023)the Provincial Natural Science Foundation of Guangdong(2023A1515011745)for financial support of this research。
文摘To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.Here,we report a low-potential photoelectrochemical(PEC)system that selectively and efficiently extracts Li metals from multi-cation electrolytes under 1 sun illumination.Based on the difference of redox potential,we can get rid of the disturbance of other cations(i.e.,Fe,Co and Ni ions)by a bias-free PEC device to realize the extraction of high-purity Li metals on a coplanar Si-based photocathode-TiO_(2) photoanode tandem device at 2 V of applied bias(far less than the redox potentials of Li^(+)/Li).In such system,the extraction rate of Li metals(purity>99.5%)exceeds 1.35 g h^(-1)m^(-2)with 90%of Faradaic efficiency.Long-term experiments,different electrode/electrolyte tests,and various price assessments further demonstrate the stability,compatibility and economy of PEC extraction system,enabling a solar-driven pathway for the recycling of critical metal resources.
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 the National Natural Science Foundation of China(52202093)Postgraduate research&practice innovation program of Jiangsu province(SJCX25_2553)+1 种基金the China Postdoctoral Science Foundation(2023M731357)the open project of Anhui Province Key Laboratory of Efficient Conversion and Solid-State Storage of Hydrogen&Electricity(ECSSHE2024KF03)。
文摘Developing selective electrodes for lithium extraction from brines remains challenging.This work reports room-temperature synthesized cubic copper hexacyanoferrate(Cu HCF)nanoparticles for hybrid capacitive deionization(HCDI).The Cu HCF framework exhibits a high surface area(715.84 m^(2)·g^(-1)),dual redoxactive sites([Fe^(Ⅲ)(CN)_(6)]^(4-)/[Fe^(Ⅱ)(CN)_(6)]^(3-)and Cu^(+)/Cu^(2+)),and excellent cyclability(99.4%capacity retention after 1000 cycles).In HCDI system,the Cu HCF cathode demonstrates remarkable Li^(+)ions selectivity,achieving a 25.5 mg·g^(-1)adsorption capacity in 500 mg·L^(-1)Li Cl solution with 94%charge efficiency at1.2 V.Notably,in mixed Li^(+)/Mg^(2+)solutions(30:1 molar ratio),Cu HCF nanoparticles maintain a high separation coefficient of 3.1,attributed to the synergistic effects of ionic sieving and preferential redox interactions.Mechanistic studies confirm Li^(+)(de)intercalation via reversible[Fe^(Ⅲ)(CN)_(6)]^(4-)/[Fe^(Ⅱ)(CN)_(6)]^(3-)and Cu^(2+)/Cu^(+)transitions.Density functional theory calculations reveal Li^(+)exhibits lower adsorption energy than Mg^(2+)(-3.72 e V vs.-1.49 e V),which fundamentally explains the preferential extraction capability of Li^(+)ions over Mg^(2+)ions during the separation process.This study advances ion-selective pseudocapacitor design for sustainable lithium extraction from high-salinity resources.
基金supported by the National Research Foundation of Korea(NRF)grants funded by the Korea government(MSIT)(Nos.RS-2024-00406500 and RS-2024-00458682).
文摘Lithium-ion batteries(LIBs)that reached their end-of-life(EoL)require recycling,rather than disposal,to recirculate valuable metals and protect the environment.This led us to investigate the extraction of metals from the cathodes of EoL lithium-titanate batteries using ethylenediaminetetraacetic acid disodium(EDTA-2Na).In this work,an orthogonal array was used to design experiments and sig-nal-to-noise calculations were used to define the optimal conditions,which were 0.50 mol/L EDTA-2Na,pH=6,75℃,180 min,2%pulp density,and 300 r/min,resulting in 97.96%,94.79%,96.45%,and 98.89%leaching efficiencies for Li,Ni,Co,and Mn,respectively.Stat-istically significant interactions between variables were then identified using Pearson’s correlation at the 95%confidence interval,and the pH and temperature were found to be significant.The extraction efficiency decreased as the pH increased,but increased as the temperat-ure increased.Machine learning fitting using linear regression for multi-output prediction was unsatisfactory,whereas random forest re-gression(RFR)produced satisfactory results.Permutation importance was computed on the fitted RFR to determine feature importance,and confirmed that the pH and temperature were influential variables;however,the time and pulp density were also noted.As the fitted RFR failed to satisfactorily predict leaching efficiencies in additional validation experiments,we recommend increasing the number of ex-periments and using additional fitting models.An additional analysis that included the initial oxidation-reduction potential(optimal 33.3 mV)revealed this to be the most important variable,the effect of which largely overshadows those of all the other variables.Finally,an environmental assessment highlighted the benefits of the chelating extraction;however,the economic assessment indicated room for improvement.
文摘An inverse spinel-type metal oxide, magnesium-manganese-titanium oxide （Mg2Mn0.5Ti0.5O4）, were prepared using the coprecipitation/thermal crystallization method. The extraction/insertion reaction with this material was investigated by X-ray, saturation capacity of exchange, pH titration, and distribution coefficient （Kd） measurement. The acid treatments of Mg2Mn0.5Ti0.5O4 caused Mg^2＋ extractions of more than 81%, whereas the dissolutions of Mn^4＋ and Ti^4＋ were less than 10%. The experimental results proved that the acid-treated sample has a capacity of exchange 56 mg·g^-1 for Li^＋ in the solution. The chemical analysis showed that the Li^＋ extraction/insertion progressed mainly by ion-exchange mechanism and surface adsorption.
基金financially supported by the National Natural Science Foundation of China(Nos.51772138,51572118,and 51601082)the Fundamental Research Funds for the Central Universities(No.lzujbky-2020-59)。
文摘Rechargeable aqueous zinc ion batteries(AZIBs)were considered as one of the most promising candidates for large-scale energy storage due to the merits of high safety and inexpensiveness.As AZIBs cathode material,Mn O_(2)possesses great merits but was greatly hindered due to the sluggish diffusion kinetic of Zn^(2+) during electrochemical operations.Herein,deep Zn^(2+) ions intercalatedδ-Mn O_(2)(Zn-Mn O_(2))was achieved by the in situ electrochemical deposition route,which significantly enhanced the diffusion ability of Zn^(2+) due to the synergistic effects of Zn^(2+) pillars and structural H;O.The resultant Zn-Mn O_(2)based AZIBs delivers a record capacity of 696 m Ah/g(0.5 m Ah/cm^(2))based on the initial mass loading,which is approaching the theoretical capacity of Mn O_(2)with a two-electrons reaction.In-situ Raman studies reveal highly reversible Zn^(2+)ions insertion/extraction behaviors and here the Zn-Mn O_(2)plays the role of a container during the charge–discharge process.Further charge storage mechanism investigations point out the insertion/extraction of Zn^(2+) and H^(+) coincides,and such process is significantly facilitated results from superior interlayered configurations of Zn-Mn O_(2)The excellent electrochemical performance of Zn-Mn O_(2)achieved in this work suggests the deep ions pre-intercalation strategy may aid in the future development of advanced cathodes for AZIBs.
文摘Electrochemical insertion/extraction of Li on cathode materials of spinel type LiMn2O4 and ordered rock-salt type LiCo0.5 Ni0.5O2 was measured on samples of which structures were well characterized. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materiaIs on electrochemical Li insertion/extraction performance was discussed. These two transition metal oxides belong to onegroup that the crystallinity of these oxides affects to the performance.
文摘Electrochemical insertion/extraction of Li on cathode materials of anatase type TiO_2, quasilayered structure V_2O_5 and layered structure MoO_3 was measured on samples of which structures were well characterized and showed a wide range of crystallinity. On the basis of experimental results on structure, morphology and charge-discharge characteristics, the effect of crystallinity of the cathode materials on electrochemical Li insertion/extraction pedermance was discussed. These three transition metal oxides were classified as one group on the basis of whether the crystallinity of these oxides affects to the performance or not; LiMn_2O_4 and LiCo_(0.5)O_2 belongs to the former group and TiO_2, V_2O_5 and MoO_3 to the latter.
基金supported by the National Natural Science Foundation of China(No.51504196)Key Research and Development Plan of Shaanxi Province(No.2017ZDXM-GY-039)
文摘The work distills the main mechanisms during the lithium insertion/extraction of LiFePO_4 cathode materials. The "diffusion-controlled" and "phase-boundary controlled" mechanism are especially illustrated. Meanwhile, some recent observation and analyses by in-situ or in operando on the Li-insertion/extraction of LiFePO_4 are summarized and prospected.
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.
基金financially supported by the National Natural Science Foundation of China(Nos.52034002,U1802253)the National Key Research and Development Program of China(No.2019YFC1908401)the Fundamental Research Funds for the Central Universities,China(No.FRF-TT-19-001)。
文摘Lithium is considered to be the most important energy metal of the 21st century.Because of the development trend of global electrification,the consumption of lithium has increased significantly over the last decade,and it is foreseeable that its demand will continue to increase for a long time.Limited by the total amount of lithium on the market,lithium extraction from natural resources is still the first choice for the rapid development of emerging industries.This paper reviews the recent technological developments in the extraction of lithium from natural resources.Existing methods are summarized by the main resources,such as spodumene,lepidolite,and brine.The advantages and disadvantages of each method are compared.Finally,reasonable suggestions are proposed for the development of lithium extraction from natural resources based on the understanding of existing methods.This review provides a reference for the research,development,optimization,and industrial application of future processes.
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.
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.
