Journal of Materials Chemistry A
·
2025
·
IF 9.5
Ning Zhang,Yuan Li,Wei Zhang,Yanling Liu,Yongjian Pei,Jie Zhao,Ping Ning,Kai Li
The effective and sustainable separation and recovery of monovalent and divalent metal ions from spent lithium-ion batteries after acid/alkali leaching still remains a big challenge to hydrometallurgical technologies. In this work, we prepared a novel crown ether-ionic liquid functionalized membrane for the selective separation of mono/divalent ions using electrodialysis (ED). a novel membrane was designed by incorporating 15-crown ether-5 (15C5), a crown ether with specific recognition for alkali metal ions, through combining interfacial polymerization and self-assembly techniques into the tunable ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4mim][NTf2]). The resultant hybrid coating forms a channel structure for the selective transport of monovalent ions. Systematic characterisations on membrane structure, physicochemical properties, and electrochemical performance were performed before and after modification. The ion transport mechanism was performed using ion diffusion mathematical modeling and density functional theory. The designed crown ether ionic liquid functionalized modified membrane 15C5-IL(2)/Cu-MPD showed excellent selectivity for various monovalent/divalent ion pairs of Li+/Mg2+, Na+/Mg2+, and K+/Mg2+ with the values of 5.33, 5.45, and 13.39, respectively. Besides, the membrane was pH-responsive, and it showed a selectivity of Li⁺/Mg²⁺ at 10.45 in the case of pH 7.5. This may be due to the synergistic effect of pore size screening brought about by the distribution of modified components and specific interactions, for instance 15C5/O--Li+. This simple approach opens a new avenue in the quest for selective IEMs for separations of certain cations by ED.
研究领域:
材料科学
·
环境工程
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
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
✓ 已验证
产品关联
DOI
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.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2022
·
IF 6.633
Junyuan Hua,Xiaohua Ma,Wenhui Ji,Quan Li,Benqiao He,Zhenyu Cui,Xiaoping Liang,Feng Yan,Jianxin Li
Ionic liquids (ILs) based liquid-liquid extraction (LLE) is one of the most efficient and green techniques for mining Li from salt lake brines, however, the extraction mechanism still needs to be clarified. Here, tributyl phosphate (TBP) and four kinds of ILs were used as extractant/co-extractant for recovering Li from Mg 2+ /Li + aqueous solution. The extraction conditions including the IL selection, IL/TBP ratio, Li + concentration and Li + /Mg 2+ ratio were analyzed in detail. A Li + recovery of 65.3 % and Li + /Mg 2+ separation factor of 68.4 at the Li + /Mg 2+ ratio of 1/50 wt% were achieved. This high Li extraction efficiency and Li + /Mg 2+ selectivity were analyzed by in-situ FTIR and 31 P NMR, the results turned out that this is attributed to the strong interactions between Li + and TBP/[NTf 2 ] − , and much larger than that of Mg 2+ . This strong interaction facilitated the [C 4 mim] + cation in IL exchange with Li + between organic and aqueous phase that finish the extraction process, which was further proved by EDX and XPS results. Additionally, the binding energy of the extraction intermediates were calculated by density functional theory (DFT), and the most stable one is 3TBP•Li•H 2 O•NTf 2 , suggesting one H 2 O combined with Li + enter into the organic phase during the extraction. As a result, the Gibbs free energy of the extraction between Li + and ILs/TBP mixture can be obtained to be −132.2 kJ mol −1 . In summary, our work showed an in-depth understanding of the extraction mechanism and provides guidelines for the ionic liquids-based Li extraction process in the future.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
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.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Cuijing Liu,Lei Li,Linbo Li,Xihong He,Hideto Matsuyama
Covalent organic framework (COF) emerges as a promising membrane material for ion separation, such as Li + extraction from brines. However, the single-functionalization of most COF channels hinders further improvements in separation efficiency. Herein, the angstrom size, positive charge and Li + affinitive sites have been integrated in the channels of triaminoguanidine (TG)-based COF membranes. Aldehydes with different lengths of oxygen-containing side chains were employed to precisely tune the size and ion affinity of the channels. Precisely engineered cationic channels with moderate pore size and Li + affinitive sites enable Mg 2+ rejection through synergistic size exclusion and Donnan exclusion, while simultaneously accelerating Li + permeation via affinitive interactions. The optimized membrane, TG-1, achieves a remarkable Li + /Mg 2+ selectivity of 423 with a Li + permeation rate of 34.02 mmol m -2 h -1 . Additionally, TG-1 is able to perform well in practical conditions including high Mg 2+ /Li + mass ratio, high temperature, long operation time and also in various mono-/divalent metals separations. This study offers insights in the construction of multi-functional membrane channels for efficient ion separations.
研究领域:
材料科学
·
化学工程
·
分离技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Le Shi,Li Ding,Sihua Liu,Haifu Gao,Jingguo She,Jianhua Zhang,Xiaolong Lu,Chunrui Wu
To achieve efficient separation of Li + /Mg 2+ , nanofiltration membranes (NFMs) with intensified positive charge density were fabricated by surface grafting of guanazole (GAZ) on the surface of piperazine (PIP)/trimesoyl chloride (TMC) NFMs. GAZ is rich in amino groups with smaller molecular size, could contact and react more sufficiently with reaction sites on membrane surface, and give less potential blockage of surface pores, compared to traditional surface grafting molecules. The influence of the chargeability and pore size of pristine PIP/TMC NFMs and surface grafting reaction on the structure and performance of GAZ grafted NFMs was investigated. Simulated brine with Mg 2+ /Li + ratio of 150 was utilized to evaluate the feasibility of GAZ grafted NFMs in treating salt-lake brine with high Mg 2+ /Li + ratios. The results showed that the positive charge density on the NFMs surface was improved and the percentage of larger pores was reduced with the successful grafting of GAZ. The optimal GAZ grafted NFMs exhibited higher MgCl 2 rejection (94.2%) than that of PIP/TMC NFMs (64.2%) and maintained a stable pure water permeance. It was worth noting that the Li + /Mg 2+ separation factor for simulated brine of 2000 mg·L -1 (Mg 2+ /Li + ratio of 150) reached 25.7, which was potentially applicable for treating salt-lake brine with high Mg 2+ /Li + ratios.
研究领域:
材料科学
·
环境工程
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
·
2025
·
IF 9.8
Fengrui Yang,Xinyu Ma,Jun Wei,Xuanhua Chen,Zhi Wang
The efficient extraction of lithium from salt-lake brine still faces challenges due to the insufficient performance of nanofiltration (NF) membranes. In this study, a nanofiltration membrane was fabricated by first pre-crosslinking polyethyleneimine (PEI) with 1,3,5-triformylphloroglucinol (Tp), followed by interfacial polymerization (IP) with trimesoyl chloride (TMC). The pre-crosslinking step incurred no amine loss. However, the higher molecular weight and increased steric hindrance of the product reduced its subsequent crosslinking with TMC. An optimal balance enables the simultaneous enhancement of both the overall crosslinking density, which is contributed by both pre-crosslinking and TMC crosslinking, and the positive charge density of the membrane. The optimized membrane (Tp 0.12) achieved a pure water permeability of 8.57 L·m −2 ·h −1 ·bar −1 and an ideal LiCl/MgCl₂ selectivity of 32.9, representing 179 % and 700 % of the values for the pristine membrane, respectively. Moreover, the optimal membrane remained effective even when the Mg 2+ /Li + ratio in the feed was as high as 140 or the total salt concentration reached up to 10,000 ppm. This work provides a simple and efficient new pathway for preparing high-performance selective nanofiltration membranes for lithium extraction.
研究领域:
材料科学
·
膜技术
·
分离科学
·
环境工程
·
锂资源回收
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
·
2026
·
IF 9.8
Mengyao Chen,Yangxiang Huang,Yeqiang Lu,Congjie Gao,Lixin Xue
Polyamide/polyethylene (PA/PE) nanofiltration (NF) membranes based on polyethyleneimine (PEI) had demonstrated excellent Li + /Mg 2+ selectivity, but showing trade-off between their permeance and Li + /Mg 2+ selectivity. In this work, a novel cross-substrate counter diffusion (CSCD) method was introduced to grow and secure ZIF-L particles in the PA layers. Specifically, rather than directly contacting the PA layers containing Zn(II) cation (PA/Zn) with an aqueous solution of 2-methylimidazole (2-MIM) ligand from the top sides, 2-MIM ligand molecules were diffused across the PE substrate from the bottom sides to react with Zn(II) secured on the top sides of PA layers. Compared with the top-down method, the bottom-up approach had yield PA/ZIF-B NF membranes with higher surface roughness, larger average pore size and narrower pore size distribution. Notably, the pure water permeance of PA/ZIF-B membrane was increased by 2.6-folds to 15.1 L·m −2 ·h −1 ·bar −1 at a high Li + /Mg 2+ separation factor (S Li/Mg ) of 16.5, breaking the trade-off performance upper bound between water permeance and Li + /Mg 2+ separating selectivity and outperforming most of the reported TFN NF membranes.
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
·
2026
·
IF 9.9
Yingying Dong,Jun Wei,Xinyu Ma,Shuwei Jia,Fengrui Yang,Zhi Wang
A novel bis-quaternary ammonium salt was synthesized. • The bis-quaternary ammonium salt was used as an aqueous co-monomer to enhance the size sieving and charge exclusion effects of the nanofiltration membrane. • The Li + /Mg 2+ separation factor of the optimized membrane reached 73.3, which is 5.4 times that of the pristine membrane. Efficient separation of Li + and Mg 2+ from salt lakes is important for the application and recovery of lithium resources. In this work, a novel bis-quaternary ammonium salt (QTMPDA) was synthesized and utilized as a co-monomer in the polyethyleneimine aqueous solution for interfacial polymerization (IP), synergistically regulating the pore structure and surface charge of the nanofiltration membrane and improving its Li + /Mg 2+ separation performance. The QTMPDA monomer features a linear short-chain diamino structure, enabling it to participate in the IP, increase the crosslinking density of the polyamide network, and form a more concentrated pore size distribution, thereby enhancing the membrane's size sieving effect. Meanwhile, the two quaternary ammonium cations in QTMPDA can effectively increase the membrane surface electropositivity, strengthening the electrostatic repulsion of Mg 2+ . Relative to the unmodified membrane, the zeta potential of the optimized membrane was elevated from −5.9 mV to 20.2 mV at pH 7 and the MgCl 2 rejection was increased from 93.3% to 99.2%. Moreover, the membrane demonstrated an excellent Li + /Mg 2+ separation factor of 73.3 (mass ratio of Mg 2+ /Li + = 100). This work offers a novel approach for regulating IP process via functional aqueous co-monomers to optimize membrane structure and performance. Download: Download high-res image (139KB) Download: Download full-size image
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2022
·
IF 9.136
Yanghe Liu,Quan Li,Shenghuan Wang,Mengzhu Liang,Yanhong Ji,Zhenyu Cui,Mohammad Younas,Jianxin Li,Benqiao He
High-performance nanofiltration (NF) membrane plays a key role in Li + /Mg 2+ separation process. In this work, a new NF membrane with positively and negatively charged groups was prepared by grafting p-aminosalicylic acid (AS) onto the surface of polyamide (PA) membrane followed by chelation with Fe 3+ ions for Li + /Mg 2+ separation. The AS grafting (PA-g-AS) and Fe 3+ chelating (PA-g-AS-Fe) NF membranes had almost same surface and section structure and surface pore size as the PA membrane. But Zeta potential (about −8 mV at pH 7) of the obtained PA-g-AS-Fe membrane was improved in comparison with the PA and PA-g-AS NF (about −20 mV at pH 7) membranes due to Fe 3+ addition, suggesting that there were positively and negatively charged groups on the membrane surface. The PA-g-AS-Fe membrane showed a high Mg 2+ rejection of 97.7% and high Li + permeation (negative rejection of −87.6%); while a high Li + /Mg 2+ separation factor (S Li , Mg ) of about 81.5 was achieved, which is much higher than those for PA and PA-g-AS NF membranes and surpassed those of the results reported in literature. The fluxes of three membranes were about the same. The results demonstrated the NF membrane with positively and negatively charged groups was suitable for efficient separation of Li + /Mg 2+ and would have promising applications in recovery of lithium from brine.
研究领域:
材料科学
·
环境工程
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
·
2026
·
IF 9.9
Jiadi Ying,Zhen Cui,Xiaoxiang Xi,Junwei Zhu,Tiancun Liu,Song Lu,Qi Shen,Min Guo,Yeqing Wang,Zhen Yang,Yaochun Chen,Minfeng Zeng,Zhixin Yu,Yuqing Lin
The selective separation of Li + from Mg 2+ in salt lake brines is critical for sustainable lithium supply but remains challenging due to their similar hydrated radii. Unlike conventional approaches that rely on a single polyelectrolyte system, this study introduces a comparative layer-by-layer (LbL) assembly strategy to systematically screen optimal polycationic building blocks. We employ two distinct polycations, polyethyleneimine (PEI) and chitosan (Cs), paired with poly(sodium 4-styrenesulfonate) (PSS) on a sulfonated poly(ether ether ketone) (SPEEK) substrate, and systematically elucidate how polycation chemistry governs membrane structure, surface charge, and ion-transport behavior across the entire LbL assembly series. The optimized PEI7.5 membrane delivers a Li + /Mg 2+ permselectivity of 9.7, a 13-fold improvement over pristine SPEEK (0.73) and a 31% enhancement over Cs7.5 (7.4), while maintaining a high Li + flux of 0.22 mol·m −2 ·h −1 . This performance represents one of the highest selectivity values reported for LbL-assembled monovalent cation exchange membranes. Combined experimental characterization and molecular dynamics simulations reveal that the superior performance of PEI-based membranes originates from synergistically enhanced denser positive charge sites and narrower pore size distribution, which collectively impose stronger electrostatic repulsion and steric hindrance against Mg 2+ . Overall, this work not only establishes a robust structure–property relationship for LbL-assembled polyelectrolyte membranes, but also provides a polycation-screening paradigm and a mechanistic framework for rationally designing next-generation cation exchange membranes toward high-efficiency lithium extraction from brines.
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）