JOURNAL OF MEMBRANE SCIENCE
·
2024
·
IF 8.4
Wubin Wang,Jin Wang,Yufei Yan,Kaili Huo,Chao Han,Qingyun Zhang
The positively charged nanofiltration (NF) membrane prepared via interfacial polymerization (IP) of polyethyleneimine (PEI) and trimesoyl chloride (TMC) has drawn considerable attention for lithium-magnesium separation, particularly crucial for lithium recovery from salt lakes with high Mg 2+ /Li + mass ratios. However, NF membranes prepared solely from amine monomers have not achieved efficient Li + and Mg 2+ separation. In this study, PEI-g-C 3 N 5 /TMC composite NF membranes were successfully fabricated by mixing amino-rich graphitic carbon nitride (g-C 3 N 5 ) with PEI, followed by the IP reaction of the mixed solution with TMC. Molecular dynamics (MD) simulation results showed that g-C 3 N 5 had an attractive effect on PEI, which led to a decrease in the diffusion rate of PEI, thereby resulting in a thinner separation layer. Density functional theory (DFT) revealed that g-C 3 N 5 competed with PEI, leading to a reduction in the crosslinking within the polyamide (PA) layer and subsequently causing an increase in the surface pore size of the membrane. Besides, the hydrophilicity and positive charge of the modified membrane were both improved. MD simulations, transition state theory, and DLVO principles indicated that the modification of the PA layer by g-C 3 N 5 enhanced the repulsion of Mg 2+ and the transport of Li + during the NF process. This breakthrough effectively overcame the trade-off effect between membrane separation and permeability, especially at a g-C 3 N 5 content of 0.06 wt%, where the lithium-magnesium selectivity coefficient ( S Li, Mg = 18.18) and pure water flux (Flux = 58.59 L m −2 h −1 ) reached the optimum values. Meanwhile, the PEI-g-C 3 N 5 /TMC membrane demonstrated stable separation performance during prolonged filtration and in solutions with varying Mg 2+ /Li + mass ratios. This study not only provides an effective strategy for the design of NF membranes but also expands the application prospects of nanomaterials in the field of membrane separation.
研究领域:
材料科学
·
环境工程
·
化学工程
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DOI
高影响因子
DESALINATION
·
2024
·
IF 8.3
Li Wang,Jianfeng Zhang,Shixin Meng,Huiyong Wu,Yunze Zhao,Zhen Meng,Lei Feng,Huanting Wang,Yuan Cheng,Liangrong Yang,Huizhou Liu
The dissolution loss of extractant into aqueous solution during lithium solvent extraction from salt lakes poses a significant issue. We found that branched chains of neutral organophosphorus extractants provide suitable steric hindrance, enhancing lithium extraction efficiency and Li/Mg selectivity. Additionally, increasing the number of alkyl chains in organophosphorus extractants increases their hydrophobicity, thereby reducing extractant dissolution loss during the extraction process. Based on these findings, a novel extraction system comprising tri(2-ethylhexyl) phosphate (TOP), FeCl 3 , and 4-methyl-2-pentanone (MIBK) was explored. The extraction conditions, including the Fe/Li molar ratio, diluents, phase ratio, and stripping conditions, were thoroughly investigated and optimized. The extraction mechanism was elucidated at the molecular level using FT-IR, Raman, NMR, and density functional theory (DFT) calculations. The results demonstrated that the TOP-FeCl 3 -MIBK system achieved an 85 % extraction efficiency for Li + in a single stage, with a Li + /Mg 2+ separation factor reaching 5842, surpassing previously reported data in the literature. 31 P NMR and 7 Li NMR analyses revealed that the TOP and tributyl phosphate (TBP) complexes existed in different forms within the organic phase. Slope analysis indicated that the stoichiometric ratio of the extraction complex involving Li + , TOP, and MIBK was LiFeCl 4 ·TOP·MIBK. Furthermore, DFT calculations indicated that the TOP complex was more stable than the TBP complex after extraction. We anticipate that our findings will pave the way for the development of a series of novel extractants with higher Li/Mg selectivity by enhancing steric hindrance and incorporating longer alkyl chains to minimize dissolution loss. We expect this research to inspire the development of similar neutral organophosphorus extractants.
研究领域:
化学工程
·
材料科学
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DOI
高影响因子
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
·
2021
·
IF 5.302
Ying Tang,Huan Li,Jie Li,Weishuang Fang,Yang Yang,Zhiyuan Zhang,Liang Fang
Ca 3- x Mg 1+ x LiV 3 O 12 (0 ≤ x ≤ 1) ceramics with cubic-garnet-structure were synthesized by the solid-phase reaction. The replacement of Ca 2+ with the smaller Mg 2+ exerted an increasingly strong “rattling” effect at the A-site of Ca 3- x Mg 1+ x LiV 3 O 12 . With increased Mg 2+ , ε r increased from 10.5 ± 0.1 to 15.4 ± 0.1 and ε corr increased from 11.0 ± 0.1 to 16.0 ± 0.1, whereas the theoretical ε th decreased from 12.0 ± 0.1 to 10.5 ± 0.1. ε corr was higher than ε th due to the “rattling” effect. The enhanced “rattling” effect caused τ f to increase rapidly from –64.1 ± 1.0 ppm/°C to +267.2 ± 1.0 ppm/°C. With increased x , Q × f decreased from 74,700 ± 500 GHz to 15,370 ± 500 GHz, due to the decreased packing fraction, increased FWHM of the A 1g modes, and enhanced “rattling” effect. Additionally, the chemical compatibility between Ca 2.75 Mg 1.25 LiV 3 O 12 and Ag electrodes was confirmed, indicating this material’s potential for LTCC .
研究领域:
材料科学
·
物理学
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2016
·
IF 7.145
Shuojian Su,Yanna NuLi,Zhenguo Huang,Qi Miao,Jun Yang,Jiulin Wang
Mg2+/Li+ hybrid batteries have recently been constructed combining a Mg anode, a Li+-intercalation electrode, and an electrolyte containing both Mg2+ and Li+. These batteries have been reported to outperform all the previously reported magnesium batteries in terms of specific capacity, cycling stability, and rate capability. Herein, we report the outstanding electrochemical performance of Mg2+/Li+ hybrid batteries consisting of a one-dimensional mesoporous TiO2(B) cathode, a Mg anode, and an electrolyte consisting of 0.5 mol L–1 Mg(BH4)2 + 1.5 mol L–1 LiBH4 in tetraglyme. A highly synergetic interaction between Li+ and Mg2+ ions toward the pseudo-capacitive reaction is proposed. The hybrid batteries show superior rate performance with 130 mAh g–1 at 1 C and 115 mAh g–1 at 2 C, together with excellent cyclability up to 6000 cycles.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
MINERALS ENGINEERING
·
2026
·
IF 6
Wanting Yang,Chenxu Wang,Yuchen Shi,Hongchang Liu,Jun Wang
High Mg 2+ induces hydrophilic deposits that passivate malachite. • Mg 2+ deposition suppresses Cu–S film formation during sulfidization. • Mixed collectors improve malachite flotation in high-Mg 2+ recycled water. • XPS, SEM–EDS and ToF-SIMS reveal Mg coverage and Cu–S film evolution. The flotation recovery of malachite from complex polymetallic ores is often severely depressed by high concentrations of Mg 2+ in recycled water; however, the underlying mechanism and effective mitigation strategy remain unclear. In this study, microflotation experiments combined with surface characterization and spectroscopic analyses were conducted to elucidate the inhibitory role of Mg 2+ in malachite sulfidization flotation and to evaluate the performance of a mixed-collector system. The results showed that in the sodium hydrosulfide (NaHS)–potassium butyl xanthate/potassium amyl xanthate (PBX/PAX) system, increasing the Mg 2+ concentration from 0 to 100 mmol/L decreased malachite recovery by 37.13%. In contrast, the addition of benzohydroxamic acid (BHA) to the PBX/PAX system markedly improved flotation recovery under high-Mg 2+ conditions. Scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM–EDS), zeta-potential, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) revealed that Mg 2+ promoted the formation of a heterogeneous Mg(OH) 2 –Cu–S composite deposit layer on the malachite surface, which blocked active Cu sites and suppressed the formation of the Cu–S sulfidized film. Contact-angle and adsorption results further showed that the synergistic interaction between BHA and PBX/PAX accelerated and enhanced collector adsorption, leading to a more stable hydrophobic surface. Fourier transform infrared (FTIR) spectra indicated that xanthates chemisorbed on Cu–S sites through Cu–S–C bond formation, whereas BHA coordinated with surface Cu 2+ via Cu–O/N chelation. Their cooperative adsorption resulted in the formation of a Cu–S/Cu–O/N composite interfacial layer, which effectively alleviated Mg 2+ -induced surface passivation. These findings demonstrated that the mixed-collector system restored the hydrophobicity and flotation performance of malachite in high-Mg 2+ water through synergistic interfacial reconstruction.
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Hongshan Wang,Guangyong Zeng,Zhaomei Yang,Xi Chen,Ludan Wang,Yuan Xiang,Xiangdong Zeng,Zhenhua Feng,Binbin Tang,Xudong Yu,Ying Zeng
With the consumption of lithium resources increasing year by year, the investigation of high-performance salt lake lithium extraction technology is extremely important. In order to effectively separate Mg 2+ and Li + from brine, a novel charge-positive nanofiltration (NF) membrane with high permeability and excellent Mg 2+ /Li + separation factor was designed by interfacial polymerization (IP) in this work. A B15C5-MX-NF membrane was fabricated by blending hydrophilic two-dimensional (2D) MXene nanosheets into a PES membrane substrate to enhance the permeability, followed by the modification of polyamide (PA) layer with a crown ether molecule (Benzo-15-crown-5) to optimize the surface properties of membrane. The PA layer thickness was effectively reduced (58 nm) due to the enhancement in the interaction between the substrate membrane and PEI by the incorporation of MXene, while the addition of B15C5 provided additional Li + permeation channels. The B15C5-MX-NF membrane exhibited excellent permeability (16.1 L·m −2 ·h −1 ·bar −1 ) and superior selectivity for Mg 2+ /Li + ( S Li, Mg of 15.8) under the dual optimization of membrane substrate and PA layer. In addition, it was demonstrated by molecular dynamics (MD) simulations that the B15C5 molecules in the B15C5-MX-NF membranes had a specific recognition ability of Li + to allow its preferential permeation, thereby enhancing the Mg 2+ /Li + selectivity of the membranes. This study provides a new idea for the preparation of NF membranes for efficient Mg 2+ /Li + separation.
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Junyuan Hua,Jintao He,Hongchang Pei,Xiaohua Ma,S. Ranil Wickramasinghe,Jianxin Li
Worldwide demand for lithium is increasing rapidly. Implementing an efficient extraction for lithium from salt-lake brines with low concentration and high Mg/Li (m/m) ratio remains challenging. A supported ionic liquid membrane (PI@14C4-SILM) contactor was developed in this work using a crown ether functionalized polyimide membrane material (Poly(DAB14C4-6FDA)) as the support and tributyl phosphate (TBP) and (1-butyl-3-methylimidazolium bis-trifluoromethylsulfonimide salt) ([C 4 mim][NTf 2 ]) mixture as the liquid phase for high-efficiency Li recovery. The results show that when the feed phase Mg/Li ratio is 35 and the stripping phase is 0.5 mol/L HCl , the Li + penetration rate, initial flux and Li/Mg selectivity of PI@14C4-SILM contactor are 0.354 μm/s, 0.128 mol/m 2 ·h and 19.1, respectively. Molecular dynamics (MD) simulation results show that Poly(DAB14C4-6FDA) and TBP have greater interaction with Li + than other ions (Na, Mg, K). Meanwhile, the binding energies of Poly(DAB14C4-6FDA)-Li-NTf 2 and TBP-Li-NTf 2 were calculated by density functional theory (DFT), which were −163.26 and −182.1 kcal/mol, respectively. The higher binding energies of the complexes indicated that their structures were more stable. The mechanism of the PI@14C4-SILM contactor's excellent Li + mass transfer performance may be the formation of a fast Li + transfer channel between the solid phase containing the crown ether structure and the liquid mobile phase in the pore structure . Besides, the TBP·Li·NTf 2 and TBP·H·NTf 2 structures in the liquid membrane phase effectively maintained the cyclic operation of the SILM system. This study provides an effective solution for selective separation of Mg/Li and utilization of Li resources in salt lake water.
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高影响因子
International Journal of Electrochemical Science
·
2023
·
IF 1.5
Kai Xia,Rui Liang,Yi Luo,Anqiao Zheng,Guodong Jiang,Mingxia Fan,Jian Xiong,Songdong Yuan
A series of LiFe 0.7 Mn 0.3−x Mg x PO 4 /C (x = 0, 0.02, 0.05, and 0.08) cathode materials were synthesized by a high-temperature solid-phase method and characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and electrochemical tests to determine the structural, morphological, and electrochemical properties of the synthesized materials. The experimental results showed that the small amount of Mg 2+ doping not only had no effect on the crystalline structure of the material but also significantly improved the electrochemical properties of the material. The LiFe 0.7 Mn 0.25 Mg 0.05 PO 4 /C material achieved specific discharge capacities of 163.2, 155.2, 149.1, and 142.0 mAh/g at 0.1C, 0.2C, 0.5C, and 1C, respectively, and a capacity retention rate of 98.6% after 50 cycles at 0.1C. It exhibited excellent rate performances and cycling stability. Electrochemical alternating-current impedance showed that the lithium-ion diffusion coefficient of the LiFe 0.7 Mn 0.25 Mg 0.05 PO 4 /C sample reached 1.19 × 10 −13 cm 2 /s, which was 4.1 times higher than that of the pre-modified sample. Combined with the cyclic voltammetry test results, it was found that the appropriate amount of Mg 2+ doping could reduce the impedance and polarization of the material as well as increase the conductivity and the lithium-ion diffusion rate, ultimately improving the electrochemical properties.
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Kuo Chen,Feiyang Li,Tao Wei,Hengyu Zhou,Tengfang Zhang,Shengchao Zhao,Tengteng Xie,Haixiang Sun,Peng Li,Q. Jason Niu
The Mg 2+ /Li + screening selectivity determines the practical application of nanofiltration technology in lithium extraction from salt-lake brines and industrial lithium production. In this work, a membrane structure design strategy based on the interlayers was developed to prepare nanofiltration (NF) membranes with high Mg 2+ /Li + separation selectivity and high permeability. Through investigating the influence of the interlayer charge on the structure and performance of the NF membrane, the interlayer for the preparation of the NF membrane with high Mg 2+ /Li + separation selectivity was screened. Relevant characterizations indicate that the positively charged interlayer can endow the NF membrane with appropriate pore size and surface charge density to achieve high Mg 2+ /Li + separation selectivity through the synergistic effect of size sieving and Donnan exclusion. Moreover, the pore size of the NF membrane is controlled by the release rate of the piperazine (PIP) from the interlayer, while the surface charge density of the NF membrane is jointly determined by the charge of the interlayer and PA layer. The performance evaluation suggests that the NF membrane prepared with the best screened interlayer has a Mg 2+ /Li + separation factor up to 88.6 while maintaining a high permeability (22.5 L m −2 h −1 ·bar −1 ), which is better than that of the most membranes reported in the literature. Overall, this work is expected to promote the practical application of NF membranes in lithium extraction from salt-lake brines and industrial lithium production.
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DOI
高影响因子
CARBOHYDRATE POLYMERS
·
2023
·
IF 11.2
Yongqin Wang,Yangze Huang,Yu Fu
Hybrid Li Mg batteries stand out by combining the rapid lithium diffusion kinetics and the advantages of magnesium. However, the uneven Mg deposits may result in continuous parasitic reactions and penetrate the separator. Herein, cellulose acetate (CA), with functional groups, was applied to engineer coordination with MOFs and construct the evenly-distributed and ample nucleation sites. Moreover, the hierarchical MOFs@CA network was fabricated via the metal ion pre-anchored strategy to regulate the uniform Mg 2+ flux and improve ion-conductivity simultaneously. Furthermore, the hierarchical CA networks with well-ordered MOFs provided efficient MOF-to-MOF ion-transportation channels and served as ion sieves to inhibit anion transportation, thereby mitigating polarization. The super dendrite-inhibition and interfacial compatibility was confirmed and the assembled Mo 6 S 8 //Mg batteries exhibited high capacity about 105 mAh g −1 and capacity decay of 4 % after 600 cycles at 30 C, which surpassed the state-of-the-art LMBs system employing Mo 6 S 8 electrode. The fabricated GPE sheds fresh strategy for the design of CA-based GPEs and bright light on the promise of high-performance LMBs.
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DOI
PubMed
高影响因子
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
·
2018
·Vol. 30
·期 1
·302-307
·
IF 2.324
Xing C. F.,Liu Q. Q.,Wu H. T.
The Li 2 (Mg 0.9 A 0.1 ) 4 TiO 7 (A = Co 2+ , Ni 2+ , Mg 2+ , Zn 2+ , Ca 2+ ) ceramics were prepared by the conventional solid-state reaction method. A series of Li 2 (Mg 0.9 A 0.1 ) 4 TiO 7 ceramics were investigated in regard to the sintering temperatures, crystal structures and dielectric properties. The Li 2 (Mg 0.9 A 0.1 ) 4 TiO 7 ceramic exhibited a single phase of Li 2 Mg 4 TiO 7 , and the Rietveld refinement was used to analyze the crystal structure. The Li 2 (Mg 0.9 Ca 0.1 ) 4 TiO 7 ceramics could be sintered below 1350 °C with high densities, high dielectric constants and near zero τ f values. The maximum Q · f value of Li 2 (Mg 0.9 Zn 0.1 ) 4 TiO 7 was higher than that of Li 2 (Mg 0.9 A 0.1 ) 4 TiO 7 (A = Co 2+ , Ni 2+ , Mg 2+ , Ca 2+ ). The optimum microwave dielectric properties of ε r = 14.77, a high Q · f value of 162,200 GHz and τ f = − 4.30 ppm/°C were achieved in Li 2 (Mg 0.9 Zn 0.1 ) 4 TiO 7 ceramic sintered at 1500 °C. In addition, Li 2 (Mg 0.9 Ca 0.1 ) 4 TiO 7 ceramic sintered at 1300 °C exhibited the suitable dielectric properties with a high ε r value of 15.79, Q · f = 100,300 GHz and a near zero τ f value of − 1.43 ppm/°C.
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Huanhuan Wu,Haoyue Zhao,Yakai Lin,Xin Liu,Lin Wang,Hong Yao,Yuanhui Tang,Lixin Yu,Haihui Wang,Xiaolin Wang
Positively charged nanofiltration membrane has gained significant interest in magnesium and lithium separation due to its separation mechanism, especially in salt lake-based lithium industry. To obtain a high-density positive charged surface and high Li + /Mg 2+ selectivity, a novel thin-film nanocomposite (TFN) nanofiltration (NF) membrane for recovery of Li + from Mg/Li mixtures with Mg 2+ /Li + ratios of 20 was successfully prepared by using polymeric amine polyethyleneimine (PEI) and monomeric amine silane coupling agent (3-diamino-methyl-cyclohexyl triethoxysilane, DTES). Then the effect of DTES on the surface properties and performance of the prepared DTES/PEI/TMC TFN membranes were investigated. Chemical composition analysis revealed that DTES not only hydrolyzed to Si–OH and then self-polymerized to Si–O–Si, but also reacted with the self-carrying acyl chloride of 1,3,5-benzene trichloromethane (TMC). Moreover, SiO 2 nanoparticles were in-situ generated from DTES inside the PA layer with high compatibility. Due to the compatible properties with the positively charged PEI polymer, the reacted DTES was distributed uniformly in the formed TFN selective layer with no noticeable aggregation. The doping of SiO 2 into the polyamide network gave rise to the enlargement of the membrane pore size, enhanced the surface hydrophilicity, and reinforced the surface positive charges. The water flux of the DTES/PEI/TMC membrane improved from 36.9 L m −2 h −1 to 49.58 L m −2 h −1 compared to the PEI/TMC membrane. Additionally, the Mg 2+ and Li + rejection of the optimized membranes was 91.46% and −10.5%, respectively, with permeability and selectivity (S Li, Mg = 12.95) superior to that of the commercial NF membranes. Considering the commercial availability of DTES, this study not only offers a high-performance nanofiltration membrane for recovering lithium from brines but also provides a feasible strategy for industrial separation of other monovalent and divalent ions.
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高影响因子
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