AICHE JOURNAL
·
2025
·
IF 4
Wenyu Shen,Yang Li,Shaoyang Gao,Yuhe Tian,Ziyun Zhang,Junbo Xu,Duo Wang,Chao Yang
Synergetic extraction system has been extensively applied in Li extraction to alleviate the increasingly severe shortage of lithium production. However, the underlying coordination mechanisms still remain unclear. Herein, a synergistic extraction system of sodium tetraphenylborate (NaBPh 4 ) and tributyl phosphate (TBP) was employed for Li + /Mg 2+ separation. With increasing TBP content in the organic phase, Li + extraction efficiency gradually rose from 88.64% to 92.20%. By contrast, Mg 2+ extraction efficiency presented an abnormal trend, which was an initial decrease followed by a gradual increase. High-resolution electrospray ionization mass spectrometry together with quantum chemical calculations revealed that Mg 2+ mainly formed Mg(BPh 4 ) 2 at the low TBP content whereas the formed complex gradually transitioned to [Mg · 4TBP](BPh 4 ) 2 with increasing TBP content, leading to the initial decline in Mg 2+ extraction efficiency. Our work provides valuable insights into the mechanisms underlying Li + /Mg 2+ separation in the TBP system and offers a promising approach for broader applications.
研究领域:
湿法冶金
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分离科学
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无机化学
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资源回收
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高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2022
·
IF 10.53
Tianrun Gu,Runnan Zhang,Shiyu Zhang,Benbing Shi,Junhui Zhao,Zhen Wang,Mengying Long,Guangzhe Wang,Ting Qiu,Zhongyi Jiang
The efficient separation of Li + /Mg 2+ is the key to lithium extraction from salt lake brine. Herein, a multi-amino quaternary ammonium salt (3,5-dimethylhydrazide-benzyl trimethyl ammonium bromide, DHTAB) was designed and synthesized to modify pristine polyamide (PA) nanofiltration membranes. DHTAB was grafted on the surface of the PA nanofiltration membrane to construct a positively selective layer for Li + /Mg 2+ separation. The introduction of DHTAB increased the membrane surface charge density to +5.16 mC m −2 , which was nearly three times that of the pristine PA membrane. The increased charge density of the modified membrane led to a stronger Donnan exclusion for Mg 2+ , and accordingly a high MgCl 2 rejection of 99.2%. The modified membranes exhibited a high Li + /Mg 2+ separation factor of up to 60.1, when applied for MgCl 2 and LiCl binary solution, which exceeded all known PA-based nanofiltration membranes.
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高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2021
·Vol. 31
·期 42
·2103214
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IF 18.808
Xianbo Yu,Guangyu Zhao,Chao Liu,Canlong Wu,Huihuang Huang,Junjie He,Naiqing Zhang
Owing to the low-cost, dendrite-free formation, and high volumetric capacity, rechargeable Li + /Mg 2+ hybrid-ion batteries (LMIBs) have attracted great attention and are regarded as promising energy storage devices. However, due to the strong Coulombic interaction of Mg 2+ with host materials, the traditional “Daniell Type” LMIBs with only Li + intercalation usually cannot ensure a satisfactory energy density. Herein, graphene monolayers are arranged intercalating into MoS 2 interlamination to construct van der Waals heterostructures (MoS 2 /G VH). This operation transforms the construction of ion channels from pristine interlamination of two MoS 2 monolayers to the interlamination of MoS 2 monolayer with graphene monolayer, thereby greatly reducing ion diffusion energy barriers. Compared with pristine MoS 2 , the MoS 2 /G VH can obviously reduce the migration energy barriers of Li + (from 0.67 to 0.09 eV) and Mg 2+ (from 1.01 to 0.21 eV). Moreover, it is also demonstrated that MoS 2 /G VHs realize Li + /Mg 2+ co-intercalation even at a rate current of 1000 mA g −1 . As expected, the MoS 2 /G VH exhibits superior electrochemical performance with a reversible capacity of 145.8 mAh g −1 at 1000 mA g −1 after 2200 cycles, suggesting the feasibility of potential applications for high-performance energy storage devices.
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高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2020
·Vol. 137
·期 47
·49549
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IF 2.52
Muhammad Awais Ashraf,Junfeng Wang,Baichun Wu,Penglei Cui,Baohua Xu,Xingchun Li
Extraction of lithium from high Mg 2+ /Li + ratio salt lake brine with the nanofiltration (NF) membrane is significantly challenging. Interfacial polymerization was utilized for the facile modification of NF membranes with polydopamine (PDA) and polyethylenimine (PEI) to enhance lithium separation efficiency. Comparing permeability and salts rejection (Li + and Mg 2+ ) of three NF membranes before and after PDA/PEI deposition, it was observed that separation efficiency was not only dependent on steric hindrance but also affected by Donnan exclusion mechanism. In the case of NF270 membrane after facile polymerization, due to small pore size distribution and low charge density confirmed by zeta potential measurements, Li + permeability was reached about 95% at a flux of 21.33 L·m −2 ·h −1 . Although with the DK membrane, separation factor SF Li/Mg was also increased up to 60 after modification, the pore narrowing effect significantly decreased lithium permeability and flux. Experimental results showed that facile modification not only enhanced stability and hydrophilicity but also reduced the high Mg 2+ /Li + ratio from 30 to 4.1 in single-stage separation.
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Yanli Zhao,Ziqi Cao,Yanxiang Liang,Zhichen Liang,Keyin Ling,Feiyan Zhou,Changsheng Guo,Yao Qian,Pengbi Liu,Xi Liu,Chunguang Wang,Mengchen Zhang,Qinglei Zhang
Membrane consisting of high-throughput aligned ion channels has been pursued for precise Li + /Mg 2+ separation. Herein, an aligned amino-functionalized γ-cyclodextrin nanofiltration membrane was fabricated via a customized interfacial polymerization technique, where the orientation of cyclodextrin ion channels was elaborately tailored by controlling the reaction conditions. The as-fabricated membrane featured ultra-thin selective layer of ∼ 26 nm, average pore size of ∼ 0.72 nm, and ultra-stable positive surface charges. In particular, the aligned intrinsic cyclodextrin cavities in the membrane offered vertical shortcuts for preferential Li + transport. Taking advantage of these, superior membrane permselectivity was achieved with the water permeance of 6.5 L·m −2 ·h −1 ·bar −1 and the Li + /Mg 2+ separation factor up to 22.5, highlighting the great potentials in lithium extraction and other ion separations. Given its simplicity and generality, this customized interfacial polymerization strategy holds great promise for manipulating aligned transport channels in thin film composite membranes, thereby enhancing their performance in a wide range of applications including, but not limited to, desalination, water purification, resource extraction, and energy conversion.
研究领域:
材料科学
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化学工程
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环境科学
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高影响因子
MACROMOLECULAR RAPID COMMUNICATIONS
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2025
·
IF 4.3
Bo Peng,Shuai Gu,Hongwei Lu,Juntao Tang,Chunyue Pan,Guipeng Yu
Developing high-efficiency antifouling nanofiltration (NF) membranes is crucial to address the dual challenges of low separation selectivity and severe membrane fouling in lithium extraction from high Mg 2+ /Li + ratio salt-lake brines. This study presents an efficient strategy based on one-step dip-coating surface modification. By grafting 1, 2-epoxy-3,3,3-trifluoropropane (TFO) molecules onto a PEI-TMC polyamide (PA) base membrane, a unique bipolar electrostatic potential reconstruction was triggered, simultaneously and significantly enhancing both the separation selectivity and antifouling performance of the membrane. In simulated high Mg 2+ /Li + ratio brine (2000 ppm, Mg 2+ /Li + = 30:1), the PA-TFO 0.75 membrane demonstrated exceptional integrated performance by achieving a high Li + /Mg 2+ selectivity of 20.5 (9.76 times higher than commercial NF membranes) while maintaining a high water permeance of 14.65 L m −2 h −2 bar −1 , and exhibiting an outstanding flux recovery ratio (FRR) approaching 100.6% (a 151% improvement over the pristine membrane), thereby meeting industrial fouling resistance standards. Critically, this strategy enabled the continuous fabrication of large-area membranes (60 m × 0.298 m). The assembled spiral-wound module (1812-type) retained a Li + /Mg 2+ selectivity of 19.5 in the same simulated brine, providing an efficient, antifouling, and scalable industrial-scale solution for lithium extraction from high Mg 2+ /Li + ratio salt lakes.
研究领域:
膜科学
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分离技术
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材料科学
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环境工程
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资源可持续回收
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DOI
PubMed
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2026
·
IF 8.8
Cuijing Liu,Bo He,Lei Li,Mengtian Bai,Zhangji Fan,Jiangfeng Song,Linbo Li,Xihong He,Hideto Matsuyama
Covalent organic frameworks (COFs) are promising candidates for fabricating ion-selective membranes towards Li + extraction from brines. However, most COF membranes feature nanoscale pores, limiting their capability to sieve angstrom-sized ions. Herein, a DG-TBB membrane with angstrom-sized, lithiophilic and positive channels was fabricated via the condensation of a small, positively charged amine (1,3-diaminoguanidine monohydrochloride, DG) with an aldehyde containing lithiophilic groups (2,4,6-trimethoxy-1,3,5-benzenetricarbaldehyde, TBB). For comparison, the DG-TFB membrane based on 1,3,5-triformylbenzene (TFB) without lithiophilic groups was adopted to clarify the role of Li + -affinitive sites, while the ODH-TBB membrane containing neutral oxalyl dihydrazide (ODH) was employed to evaluate charge effect. Benefiting from the synergistic effects of Li + affinity and Donnan exclusion, DG-TBB membrane delivered the highest Li + permeation rate of 73.6 mmol m −2 h −1 and Li + /Mg 2+ selectivity of 1200, which were superior to DG-TFB (4.3 mmol m −2 h −1 , selectivity of 238) and ODH-TBB (64.9 mmol m −2 h −1 , selectivity of 39). Moreover, DG-TBB exhibited robust separation performance in diverse practical scenarios and for various mono-/divalent cations. This study demonstrates that the rational integration of angstrom-sized pores, lithiophilicity and positive charge into COF channels enables highly efficient ion separation.
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高影响因子
AICHE JOURNAL
·
2026
·
IF 4.4
Haojie Chen,Zong Lu,Yanna Wu,Zhengyi Huang,Yuhang Zhang,Meng Zhang,Shuming Li,Jing Wang,Yanying Wei,Haihui Wang
With growing demand for lithium resources, developing high-performance Li + /Mg 2+ separation methods for salt-lake brines has become crucial, especially the highly efficient energy-saving membrane technology. For the traditional nanofiltration (NF) membranes for mono−/multivalent ion separation, achieving simultaneously high permeance and selectivity for lithium extraction from brine remained a critical challenge. Herein, we proposed a kind of cationic covalent organic frameworks (COF), TpEBr nanosheets with positive charge and structural regulation capability as dual-functional regulator for polyamide (PA) NF membranes. The introduction of TpEBr as additive reduced the diffusion rate of polyethyleneimine (PEI), forming a thin and loose membrane. Additionally, quaternary ammonium groups on TpEBr increased the membrane's surface Zeta potential, significantly strengthening the Donnan exclusion effect. The optimized membrane exhibited a significant Li + /Mg 2+ selectivity of 46.4 with a 25% increase in permeance. Such dual-functional regulation strategy for constructing high-performance NF membranes proposed in this work is promising for future highly efficient lithium extraction from brines.
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高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2026
·
IF 9.1
Wei Yang,Ping Xiong,Yinghong Wang,Tao Tao,Xuerui Liu,Xiaoling Xu,Caiyun Yang,Liming Yang,Huiji Xiao,Kai Zhang,Wei Zhang,Xubiao Luo
Membrane separation technology serves as an essential approach for the efficient and sustainable extraction of lithium from salt-lake brines, whose effectiveness crucially depends on the selective Li + /Mg 2+ separation performance. However, conventional nanofiltration (NF) membranes remain constrained by the trade-off between water permeability and ion selectivity. In this study, we proposed a two-step fabrication strategy that couples solution deposition with interfacial polymerization (IP), successfully constructing a positively charged Zr-His/PTF composite NF membrane with a thin selective layer and uniform pore size. Hydrated zirconia clusters (hydrous-ZrO 2 ) derived from inorganic zirconium salts were utilized to regulate the distribution of reaction sites via electrostatic anchoring, while the amphipathic structure of histidine was employed to restrict the diffusion of aqueous monomers. These two components synergistically modulated the IP process, enabling the precise regulation of the selective layer microstructure while significantly reducing organic reagent consumption. Under a high Mg 2+ /Li + mass ratio of 30:1, the modified membrane achieved a synchronous enhancement in Li + /Mg 2+ separation selectivity (29.57) and water permeance (21.7 L·m −2 ·h −1 , 6 bar). Moreover, the membrane maintained stable separation performance and structural integrity across a wide Mg 2+ /Li + mass ratio range (1:1 to 100:1) and throughout 100 h of continuous operation. Through the integration of fabrication methods, this study provides a straightforward, low-cost and environmentally friendly strategy for fabricating high-performance NF membranes.
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高影响因子
Advanced Science
·
2024
·
IF 14.3
Wentong Meng,Sifan Chen,Pu Chen,Feng Gao,Jianguo Lu,Yang Hou,Qinggang He,Xiaoli Zhan,Qinghua Zhang
Positively charged nanofiltration membranes have attracted much attention in the field of lithium extraction from salt lakes due to their excellent ability to separate mono- and multi-valent cations. However, the thicker selective layer and the lower affinity for Li + result in lower separation efficiency of the membranes. Here, PEI-P membranes with highly efficient Li + /Mg 2+ separation performance are prepared by introducing highly lithophilic 4,7,10-Trioxygen-1,13-tridecanediamine (DCA) on the surface of PEI-TMC membranes using a post-modification method. Characterization and experimental results show that the utilization of the DCA-TMC crosslinked structure as a space-confined layer to inhibit the diffusion of the monomer not only increases the positive charge density of the membrane but also reduces its thickness by ≈35% and presents a unique coffee-ring structure, which ensures excellent water permeability and rejection of Mg 2+ . The ion–dipole interaction of the ether chains with Li + facilitates Li + transport and improves the Li + /Mg 2+ selectivity ( S Li,Mg = 23.3). In a three-stage nanofiltration process for treating simulated salt lake water, the PEI-P membrane can reduce the Mg 2+ /Li + ratio of the salt lake by 400-fold and produce Li 2 CO 3 with a purity of more than 99.5%, demonstrating its potential application in lithium extraction from salt lakes.
研究领域:
材料科学
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环境工程
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产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Yingzhen Wu,Enshen Shi,Haojie Song,Lu Li,Chungang Xie,Yongjiang Yu,Yanan Liu,Zhongyi Jiang
Nanofiltration membranes possess great potential in ion separation, meanwhile, the pore and surface properties determining membrane permeance and selectivity, should be designed and regulated. Herein, we utilized reactive ionic liquid (1-aminoethyl-3-methylimidazolium tetrafluoroborate, AMIM-BF 4 ) simultaneously as aqueous phase additive and surface modifier to regulate pore and surface properties for fast and efficient Li + /Mg 2+ separation. AMIM-BF 4 was added in aqueous phase to undergo a competitive interfacial polymerization with polyethyleneimine (PEI), effectively increasing the average pore size of the membrane. Then, amino group in AMIM-BF 4 could react with the unreacted acyl chloride groups to modify membrane surface, increasing its positive charge and hydrophilicity. Accordingly, the membrane possessed high water permeance of 33.3 L m −2 h −1 bar −1 with MgCl 2 rejection rate of 98.9%, and separation factor of 22.7 for the mixed solution with magnesium-to‑lithium ratio (MLR) of 50:1. Meanwhile, during the 168-h continuous cross-flow test, the rejection rate for MgCl 2 remained above 98.1% with stable water permeance. Moreover, through the three-stage nanofiltration experiment, the membrane could reduce the MLR of simulated salt lake brine with 2000 ppm from 50:1 to only 0.02:1, demonstrating its potential for efficient lithium enrichment from complex brine.
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高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Zhiyuan Yi,Kai Qu,Linlong Zhou,Qing Li,Zhi Xu
Metal-organic framework (MOF) glasses offer promising potential for membrane-based separations due to their excellent processability and structural versatility. However, their inherently disordered pore structures often lead to reduced porosity and limited ion transport performance. Here, we present a controlled unzipping polymer decomposition (CUPD) strategy for fabricating ZIF-62-based glass membrane featuring interconnected and negatively charged transport channels. Polystyrene sulfonic acid (PSS) is introduced as a sacrificial porogen during the melt-quenching process, wherein partial decomposition of its carbon backbone templates the formation of interconnected micropores. Simultaneously, the sulfonate groups stabilized by coordination with Zn sites, imparted negative surface charge to the channels, facilitating the selective ions transport. The optimized membrane fabricated by CUPD strategy achieves a Li + permeation rate of 0.64 mol m −2 h −1 , which is 60-fold higher than that of the pristine ZIF-62 glass membrane. This work provides a novel inspiration for constructing MOF-based membranes with interconnected channels with tunable property for advanced ion separation applications.
研究领域:
材料科学
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膜分离技术
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无机非金属材料
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化学工程
·
离子传输
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DOI
高影响因子
危险品化学品经营许可证（带存储）