Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for...Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for more than 60%of the global lithium resources.However,structural collapse,facile deactivation during desorption process,and ultra-low actual adsorption capacity limit its further large-scale application,particularly in low-grade sulfate-type brines.Herein,considering its advantages,limitations,and structural features,the structural collapse of the aluminum-based lithium adsorbent was effectively suppressed by the in situ intercalation of VO_(3)^(-)and V_(2)O_(7)^(4-)into the interlayer of[LiAl_(2)(OH)_(6)]^(+).Evidently,the initial adsorption capacity andα_(Mg)^(Li)of as-configured adsorbents powder are 14.96 mg g^(-1) and 192.42 in real sulfate-type West Taijinar Salt Lake brines following NaCl salts removal with 800 mg L^(-1) Li^(+)and 9.56 g L^(-1) SO_(4)^(2-).Furthermore,the initial and retained adsorption capacities of these novel adsorbents granulate in brines after 100 adsorption/desorption cycles are 26.68 and 10.36 mg g^(-1),respectively,which are almost 10 times higher than those of industrially utilized products.Based on experiments and density functional theory calculations,the process and mechanism of anion intercalation control were preliminarily elucidated.Furthermore,research findings indicate that intercalated anions can influence not only interlayer interactions but also the backbone strength of LDH-type adsorbents.This work significantly overcomes the major utilization challenges of aluminum-based lithium adsorbents,thereby enabling the high-efficiency and stable extraction of Li^(+)from low-grade brines,including sulfate-type brines.展开更多
Electrochemical liquid lithium extraction technology has attracted much attention because of its high selectivity,good efficiency,and eco-friendliness.However,the low energy density per unit area and poor stability of...Electrochemical liquid lithium extraction technology has attracted much attention because of its high selectivity,good efficiency,and eco-friendliness.However,the low energy density per unit area and poor stability of traditional thin film electrodes(F-LMO),as well as manganese dissolution loss induced by the Jahn-Teller distortion of LiMn_(2)O_(4),hinder their industrial scalability.Herein,a durable and high-efficiency multistage porous LiMn_(2)O_(4) thick electrode was prepared sustainably by 3D printing technology(3DPLMO)for enhancing lithium recovery from salt lake brine.The multistage porous structure reduced the mass transfer resistance and shortened the ion diffusion path,which was conducive to accelerating the diffusion rate of Li+.Simultaneously,the three-dimensional conductive networks composed of reduced graphene oxide(r GO)and carbon nanotubes(CNT)synergized with the multistage pores effectively weakened the polarization phenomenon of the electrode and improved the stability of 3DP-LMO.The3DP-LMO exhibited a 5.5-fold higher extraction capacity per unit area and the Mn dissolution loss rate was only 1/15 compared with the F-LMO.Notably,the capacity retention rate of 3DP-LMO was 87.6%,significantly better than that of F-LMO(66.3%).Based on the quasi-in situ X-ray Diffraction results,the mechanism of lithium intercalation and deintercalation in 3DP-LMO was elucidated.Furthermore,lithium extraction parameters were optimized using response surface method-center composite design(RSM-CCD),resulting in an increase in lithium extraction capacity to 15.66 mg g^(-1)and a reduction in energy consumption to only 12.33 Wh mol^(-1).The results show that 3DP-LMO has significantly improved lithium extraction performance and stability,and has considerable prospects in practical application.展开更多
基金supported by the Sichuan Provincial Department of Science and Technology Project (2025YFHZ0271).
文摘Owing to its excellent eco-friendliness and facile water elution properties,aluminum-based lithium adsorbents have attracted a surge of interest for selectively extracting Li^(+)from Salt Lake brines,which account for more than 60%of the global lithium resources.However,structural collapse,facile deactivation during desorption process,and ultra-low actual adsorption capacity limit its further large-scale application,particularly in low-grade sulfate-type brines.Herein,considering its advantages,limitations,and structural features,the structural collapse of the aluminum-based lithium adsorbent was effectively suppressed by the in situ intercalation of VO_(3)^(-)and V_(2)O_(7)^(4-)into the interlayer of[LiAl_(2)(OH)_(6)]^(+).Evidently,the initial adsorption capacity andα_(Mg)^(Li)of as-configured adsorbents powder are 14.96 mg g^(-1) and 192.42 in real sulfate-type West Taijinar Salt Lake brines following NaCl salts removal with 800 mg L^(-1) Li^(+)and 9.56 g L^(-1) SO_(4)^(2-).Furthermore,the initial and retained adsorption capacities of these novel adsorbents granulate in brines after 100 adsorption/desorption cycles are 26.68 and 10.36 mg g^(-1),respectively,which are almost 10 times higher than those of industrially utilized products.Based on experiments and density functional theory calculations,the process and mechanism of anion intercalation control were preliminarily elucidated.Furthermore,research findings indicate that intercalated anions can influence not only interlayer interactions but also the backbone strength of LDH-type adsorbents.This work significantly overcomes the major utilization challenges of aluminum-based lithium adsorbents,thereby enabling the high-efficiency and stable extraction of Li^(+)from low-grade brines,including sulfate-type brines.
基金supported by the National Key R&D Program of China(No.2022YFE0208300)the National Natural Science Foundation of China(No.22278426)+2 种基金the China National Funds for Distinguished Young Scientists(No.22425808)the China Postdoctoral Science Foundation(No.2025M771155)the Science Foundation of China University of Petroleum,Beijing(Nos.2462024XKBH001,2462022YJRC003,2462022YJRC002,2462025BJRC002)。
文摘Electrochemical liquid lithium extraction technology has attracted much attention because of its high selectivity,good efficiency,and eco-friendliness.However,the low energy density per unit area and poor stability of traditional thin film electrodes(F-LMO),as well as manganese dissolution loss induced by the Jahn-Teller distortion of LiMn_(2)O_(4),hinder their industrial scalability.Herein,a durable and high-efficiency multistage porous LiMn_(2)O_(4) thick electrode was prepared sustainably by 3D printing technology(3DPLMO)for enhancing lithium recovery from salt lake brine.The multistage porous structure reduced the mass transfer resistance and shortened the ion diffusion path,which was conducive to accelerating the diffusion rate of Li+.Simultaneously,the three-dimensional conductive networks composed of reduced graphene oxide(r GO)and carbon nanotubes(CNT)synergized with the multistage pores effectively weakened the polarization phenomenon of the electrode and improved the stability of 3DP-LMO.The3DP-LMO exhibited a 5.5-fold higher extraction capacity per unit area and the Mn dissolution loss rate was only 1/15 compared with the F-LMO.Notably,the capacity retention rate of 3DP-LMO was 87.6%,significantly better than that of F-LMO(66.3%).Based on the quasi-in situ X-ray Diffraction results,the mechanism of lithium intercalation and deintercalation in 3DP-LMO was elucidated.Furthermore,lithium extraction parameters were optimized using response surface method-center composite design(RSM-CCD),resulting in an increase in lithium extraction capacity to 15.66 mg g^(-1)and a reduction in energy consumption to only 12.33 Wh mol^(-1).The results show that 3DP-LMO has significantly improved lithium extraction performance and stability,and has considerable prospects in practical application.
