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
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
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
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
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
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
Viewing the problem of high ene rgy consumption in the process of recovering rare earths from rare earth molten salt electrolysis slag,an environmentally friendly and low carbon process by sub-molten salt decompositio...Viewing the problem of high ene rgy consumption in the process of recovering rare earths from rare earth molten salt electrolysis slag,an environmentally friendly and low carbon process by sub-molten salt decomposition was developed.The thermodynamic analysis of sub-molten salt reaction indicates that the recovery of rare earths from the slag using sub-molten salt medium is thermodynamically feasible.In this process,the rare earth fluoride and lithium in the slag are almost transformed into rare earth hydroxide,sodium fluoride and lithium hydroxide,fluorine and lithium are transferred into the washing solution,and the rare earths in the residues can be leached into solution by acid leaching.Under the optimum reaction conditions of reaction temperature 200℃,reaction time 3 h,NaOH initial concentration 80%,NaOH-Slag mass ratio 3:1,the leaching efficiency of rare earths,fluorine and lithium can reach to 99.05%,98.23% and 99.22%.After evaporation,the fluorine and lithium in the washing solution can be obtained in the forms of sodium fluoride and lithium fluoride,the recovery efficiency reach 95.5%and 92.8%,respectively.The RE oxides(99.53%) can be obtained from the leaching solution after precipitation and roasting.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
Three ionic liquids（ILs）, namely, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-me- thylimidazolium bis[（trifluoromethyl）sulfonyl]imide and 1-ethyl-3-methylimidazolium bis[（trifluoromethyl）sul- fony...Three ionic liquids（ILs）, namely, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-me- thylimidazolium bis[（trifluoromethyl）sulfonyl]imide and 1-ethyl-3-methylimidazolium bis[（trifluoromethyl）sul- fonyl]imide with the triisobutyl phosphate（TIBP） and kerosene system were respectively used to extract lithium ion from salt lake brine with a high concentration ratio of magnesium and lithium experimentally. Results indicate that the highest extraction selectivity for lithium was obtained with IL 1-ethyl-3-methylimidazolium bis[（trifluoromethyl）- sulfonyl]imide. The effects of solution pH and phase ratio R（O/A） on the extractive step and the influence of acid concentration of the stripping solution and R（O/A） on the back extraction step were also investigated systematically. The single-step extraction efficiency of lithium ion was 83.71% under the optimal extraction conditions, and the single-step back extraction efficiency was 85.61% with a 1.0 mol/L HCI in 1.0 mol/L NaCI medium as stripping agent at R（O/A）=2. The liquid-liquid extraction mechanism and the complex of the ligand with lithium were proposed.展开更多
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Project supported by the National Key Research and Development Project (2018YFC1903400)the Jiangxi Province Graduate Student Innovation Special Fund Project (203200800389)+2 种基金the Natural Science Foundation of Jiangxi Province (20224BAB204038,20202BAB214014)the Young Elite Scientists Sponsorship Program by CAST (2022QNRC001)the Open Project of Guangxi Key Laboratory of Nonferrous Metals and Characteristic Materials Processing(2022GXYSOF11)。
文摘Viewing the problem of high ene rgy consumption in the process of recovering rare earths from rare earth molten salt electrolysis slag,an environmentally friendly and low carbon process by sub-molten salt decomposition was developed.The thermodynamic analysis of sub-molten salt reaction indicates that the recovery of rare earths from the slag using sub-molten salt medium is thermodynamically feasible.In this process,the rare earth fluoride and lithium in the slag are almost transformed into rare earth hydroxide,sodium fluoride and lithium hydroxide,fluorine and lithium are transferred into the washing solution,and the rare earths in the residues can be leached into solution by acid leaching.Under the optimum reaction conditions of reaction temperature 200℃,reaction time 3 h,NaOH initial concentration 80%,NaOH-Slag mass ratio 3:1,the leaching efficiency of rare earths,fluorine and lithium can reach to 99.05%,98.23% and 99.22%.After evaporation,the fluorine and lithium in the washing solution can be obtained in the forms of sodium fluoride and lithium fluoride,the recovery efficiency reach 95.5%and 92.8%,respectively.The RE oxides(99.53%) can be obtained from the leaching solution after precipitation and roasting.
基金the National Natural Science Foundation of China for financial support(No.91962219).
文摘The demand for lithium resources is increasing sharply with the rapid development of electric vehicles.It is of great economic significance to expand the geological resources of lithium and improve the utilization rate of lithium-containing salt lakes.In this paper,the hydrochemical types of the lithium-containing salt lakes in the Tibet Plateau were classified according to a large amount of hydrochemical data obtained from a recent investigation on the Tibet Plateau.In addition,the lithium extraction methods used in the salt lakes within each hydrochemical type area were analyzed and summarized,which provided a reference for the selection of lithium extraction processes in the same hydrochemical type of lithium-containing salt lakes in the future.The binding energies of Li(l)and anions in salt lakes with different hydrochemical types were calculated by density functional theory,which provides the theoretical basis for selecting the best lithium extraction technology in different salt lakes.We emphasize that the process with the combined characteristics of high efficiency,economy and environmental protection should be selected according to the hydrochemical type of different salt lakes.In the future,different salt lakes should focus on direct lithium extraction technology from the original brine.
基金Supported by the National Natural Science Foundation of China（Nos.21276194, U1407113）, the Training Program for Changjiang Scholars and Innovative Research Team in University, China（No.[2013]373） and the Innovative Research Team of Tianjin Municipal Education Commission, China（No.TD12-5004）.
文摘Three ionic liquids（ILs）, namely, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-me- thylimidazolium bis[（trifluoromethyl）sulfonyl]imide and 1-ethyl-3-methylimidazolium bis[（trifluoromethyl）sul- fonyl]imide with the triisobutyl phosphate（TIBP） and kerosene system were respectively used to extract lithium ion from salt lake brine with a high concentration ratio of magnesium and lithium experimentally. Results indicate that the highest extraction selectivity for lithium was obtained with IL 1-ethyl-3-methylimidazolium bis[（trifluoromethyl）- sulfonyl]imide. The effects of solution pH and phase ratio R（O/A） on the extractive step and the influence of acid concentration of the stripping solution and R（O/A） on the back extraction step were also investigated systematically. The single-step extraction efficiency of lithium ion was 83.71% under the optimal extraction conditions, and the single-step back extraction efficiency was 85.61% with a 1.0 mol/L HCI in 1.0 mol/L NaCI medium as stripping agent at R（O/A）=2. The liquid-liquid extraction mechanism and the complex of the ligand with lithium were proposed.
