DALTON TRANSACTIONS
·
2018
·Vol. 47
·期 11
·3864-3871
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IF 4.099
Aolei Gao,Zhenhua Sun,Shaopeng Li,Xinjuan Hou,Huiquan Li,Qisheng Wu,Xinguo Xi
Li1.6Mn1.6O4 is a representative ion sieve material that is used to recover lithium from salt brines and bitterns owing to its high lithium ion adsorption capacity reaching 11.9–44 mg g−1. However, manganese dissolution during acid treatment hinders the industrial application of the material. For investigating the mechanism of manganese dissolution, the precursor Li1.6Mn1.6O4 and ion sieve H1.6Mn1.6O4 were prepared and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), chemical content analyses, diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS), and X-ray photoelectron spectroscopy (XPS). The results of XRD, SEM, and FT-IR showed that the bulk phase of Li1.6Mn1.6O4 retained the spinel structure, whereas the lattice diminished during acid treatment. The results of chemical content analyses showed that the bulk phase of Li1.6Mn1.6O4 contained a few trivalent manganese atoms and that the mean valence of manganese in the material increased during acid treatment. DRIFTS and XPS exhibited that the surface of Li1.6Mn1.6O4 was mostly full of tetravalent manganese and retained the spinel structure during acid treatment. In the proposed mechanism of manganese dissolution, an electron of trivalent manganese in the bulk phase transfers to the surface and is captured by tetravalent manganese within the acidic environment. Then, tetravalent manganese is converted to bivalent manganese after acquiring sufficient electrons, and dissolution occurs simultaneously.
研究领域:
材料科学
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化学工程
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
·
IF 16.744
Guotai Zhang,Chunxi Hai,Yuan Zhou,Weiping Tang,Jingze Zhang,Jinbo Zeng,Yanhua Liu,Shengde Dong,Guiping Peng
A surge of interest has been attracted by Li 1.6 Mn 1.6 O 4 -type adsorbent for collecting lithium resources from salt-lake brines due to its excellent selectivity, high theorical adsorption capacity up to 72. 3 mg g −1 and low cost. However, its large-scale practical application is limited because of its bone element Mn dissolution during the cycled desorption process. Herein, F and Al co-modifying technique, an efficient method for stabilizing its spinel structure or forming protective coating, was employed to improve the application performances of Li 1.6 Mn 1.6 O 4 -type adsorbent prepared by sol–gel method. Based on the various characterization results, the co-modification not only leads to the formation of fluoride-rich coating and the substitution of Mn 3+ by Al 3+ , but also generates the active adsorbents with abundant nano-islands. DFT calculations revealed that the coating layer is indeed AlF 3 rather than LiF. In addition, in-situ high-temperature XRD tests demonstrates that the co-modification can significantly enhance the heat resistance and structural stability of the material. As-prepared adsorbent exhibits greatly improved Li adsorption capacity (increased from 28.5 to 33.7 mg g −1 ), lower Mn loss rate (decreased from 2.1 to 1.8%), enhanced cycling stability and good adsorption selectivity in the Qarhan brine containing Na + , K + , Ca 2+ , Mg 2+ , which is very significant and important for effectively removing lithium from low-grade brines.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
·
2021
·Vol. 69
·期 2
·289-300
·
IF 1.967
Fu Liu,Weifang Zhu,Minmin Gou,Hengheng Cao,Ruili Guo
Two-dimensional flake Li 1.6 Mn 1.6 O 4 (LMO) was added to the Pebax®MH 1657 (Pebax) matrix to prepare mixed-matrix membranes (MMMs) for CO 2 /CH 4 mixed gas separation. The average pore diameter of the LMO nanosheet was about 10.79 nm: a fast CO 2 transport channel could be established in the membrane. In addition, the Li and oxygen defect site (O δ− ) in the LMO had an affinity for CO 2 , which improved the permeability of the membrane and the selectivity for CO 2 separation. Furthermore, the ultrathin structure of LMO with large aspect ratio was also conducive to gas separation. When the LMO filling amount was 2.0 wt%, the permeation rate of pure CO 2 gas of Pebax/LMO-2.0 membrane was 117.9 Barrer, and the CO 2 /CH 4 ideal selectivity was 18.74, which were 119.7 and 35.8% higher than Pebax membrane, respectively. The CO 2 /CH 4 mixed gas separation results of Pebax/LMO-2.0 membrane showed that the CO 2 permeability and CO 2 /CH 4 selectivity were 158.54 Barrer and 33.41, respectively, and were increased by 83.24 and 23.15%, compared with Pebax membrane.
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
高影响因子
HYDROMETALLURGY
·
2021
·
IF 4.156
Luri Bao,Jingze Zhang,Jie Wu,Guotai Zhang,Yang Yang,Weiping Tang,Mei Xue
Owing to the increasing global demand for lithium, extraction of lithium from salt lake brine water has received considerable attention. In this study, the magnesium doping to produce Li 1.6 Mg x Mn 1.6-x O 4 (LMMO) was designed to overcome the limitation caused by the loss of Mn due to dissolution. The chemical and morphological properties of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The XRD results confirmed that the crystal structure of Li 1.6 Mn 1.6 O 4 was retained after Mg-doping. Scanning electron microscopy and energy-dispersive X-ray spectroscopy showed that LMMO has a flake-shaped structure and the Mg 2+ ions were uniformly distributed in the precursor. The doping of Mg 2+ led to the decrease of Mn 3+ content in the precursor, improving its structural stability. The adsorption capacity of LMMO-6% was 35.6 mg g −1 , which was greater than that of the undoped sample (33.2 mg g −1 ). After the tenth cycle, the dissolution loss of Mn in LMMO-6% was 0.55%, and it is smaller than that for lithium manganese oxide (0.94%). Results confirm that the structural stability was improved compared to undoped adsorbents. Moreover, batch adsorption experiments demonstrated the potential of the HMMO-6% adsorbent to be used for lithium adsorption from real salt lake brine.
研究领域:
材料科学
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环境科学
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产品关联
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
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2025
·
IF 3.9
Chen Zheng,Liu Peng,Cao Yu-Long,Xie Yu-Long
The manganese-based ion sieve H 1.6 Mn 1.6 O 4 shows significant advantages in lithium adsorption. Its prominent features include high adsorption capacity and low pollution characteristics of the preparation process. These combined advantages make this material important in the lithium extraction technology in salt lakes. However, problems such as high manganese dissolution loss rate, poor cyclic stability, and difficulty in powder recycling seriously restrict the industrialized application. In this paper, we propose to optimize the structure of spinel-type manganese lithium ion-sieves with a 2% Co 3+ doping strategy, which can effectively inhibit the lattice collapse triggered by Jahn–Teller aberration during the pickling cycle by replacing part of the Mn 3+ active sites with Co 3+ . After doping, the relative Mn 4+ content on the surface of the material increased from 58%–61% according to the XPS test, confirming that the introduction of Co 3+ facilitated the transition of Mn 3+ to the higher valence state Mn 4+ through the charge compensation effect. Reducing the disproportionation activity of Mn 3+ reduces the dissolution loss of Mn 2+ during the pickling process. The experimental results showed that the adsorption of doped HMCO-2 material increased from 28.8–34.9 mg/g. The adsorption capacity retention rate was 77% after five cycles, there was a high selective adsorption of Li + , and the manganese dissolving loss rate was decreased to 2.3%.
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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无机化学
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Yunhao Wang,Junxiang Zhang,Zeyu Cheng,Xu Xiang
Lithium extraction from salt-lake brine is important to ensure a sustainable supply of lithium and meet its increasing demand for use in electric vehicles and large-scale energy storage devices. However, it remains challenging to separate Li+ ions from coexisting ions in the brine. Here, we propose a combined strategy of a core–shell structure and hydrophilic modification of a Li1.6Mn1.6O4 electrode to efficiently extract lithium from brine with a high sodium ion content. Core–shell Li1.6Mn1.6O4@carbon was derived from polydopamine-encapsulated Li1.6Mn1.6O4 via calcination. The ∼2 nm carbon shell protects Mn from leaching during lithium extraction. Compared with bare Li1.6Mn1.6O4, the lithium extraction capacity of the modified electrode increases from 20 to 39.6 mg/g in a brine with a high Na–Li ratio (Na/Li = 44.78 by weight). The coating of polydopamine on the Li1.6Mn1.6O4@carbon electrode reduces the water contact angle from 119 to 86.9°, resulting in a hydrophilic surface. Using an electrochemical adsorption method, the lithium extraction capacity and desorption ratio reach 65.6 mg/g and 86.0%, respectively, which are superior to the performance of the current membrane capacitive deionization and electrochemical method. The modified electrode shows high lithium-ion selectivity and excellent stability due to the reversible redox reactions during lithium extraction/release. The strategy proposed here provides insights into the structural design of electrodes for the highly efficient separation of lithium from brine.
研究领域:
材料科学
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电化学
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能源存储
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环境工程
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产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 36
·20878-20890
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IF 10.733
Aolei Gao,Xinjuan Hou,Zhenhua Sun,Shaopeng Li,Huiquan Li,Jianbo Zhang
Spinel-type lithium manganese oxides (LMOs) are the most promising lithium-adsorption materials. LMOs can be in the form of solid solutions of LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4. However, uncertainty about the lithium-desorption mechanism restricts material development. The synthesis of intermediate products of spinel-type LMOs during acid treatment is important to investigate such a mechanism. In this work, precisely controlled acid treatment experiments were performed to successfully obtain the intermediate products of LiMn2O4, Li1.33Mn1.67O4, and Li1.6Mn1.6O4. For LiMn2O4, lithium was desorbed with the dissolution of manganese. For Li1.33Mn1.67O4 and Li1.6Mn1.6O4, the lithium-desorption mechanism was an ion-exchange reaction, where lithium ions (Li+) in the 8a sites were prioritized for the ion-exchange reaction compared with Li+ in the 16d sites. Density functional theory (DFT) calculation results confirmed the experimental results and explained that the prioritization of Li+ in the 8a sites arose from its lower reaction-energy barrier, thereby revealing that Li+ preferred to move to the nearest vacant 8a sites when lithium was desorbed because of the lower diffusion-energy barrier. This work is the first to clarify the lithium-desorption mechanism through experiments and DFT calculations, and thus lays a foundation for the further exploitation of LMOs.
研究领域:
材料科学
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电化学
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计算化学
✓ 已验证
DOI
高影响因子
DESALINATION
·
2025
·
IF 9.8
Zhangfa Yu,Panmin Yang,Chunxi Hai,Xuequn Li,Hongbo Sun,Yuan Zhou,Longgang Li,Xudong Yu,Wanghai He,Ying Zeng
Li 1.6 Mn 1.6 O 4 -type adsorbents show significant promise for lithium resource extraction from complex saline lakes due to their exceptional selectivity and high theoretical adsorption capacity of 72.3 mg g −1 . However, their practical application is markedly constrained by rapid manganese dissolution during elution with dilute HCl, primarily attributed to Jahn-Teller effect-induced Mn O structural distortion. To address this limitation, a synergistic S 2− /Na + co-doping strategy was employed: Na + stabilizes the spinel structure via Na O bond formation, while S 2− doping enhances charge density. In situ XRD analysis elucidated the structural evolution of the doped material. Experimental results demonstrate that H 1.6 Mn 1.6 O 4 modified with 1 % Na 2 S achieves an adsorption capacity of 39.6 mg g −1 in 300 ppm LiOH solution, with manganese dissolution loss below 2 %, and attains a single-pass lithium extraction efficiency of 99.5 % from oilfield brine containing 100 ppm Li + . Furthermore, the influence of Na + concentration on Li + adsorption selectivity was investigated for the first time, and the underlying mechanism was summarized. This finding is highly significant for efficient lithium extraction from various brines.
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DOI
高影响因子
Particuology
·
2025
·
IF 4.3
Yiying Wang,Dandan Shi,Yue Cao,Xing Han,Tianying Zhang,Kaipeng Zhong,Qi Zhao,Naicai Xu,Shaoju Bian
Driven by the increasing global demand for lithium, significant attention has been directed toward developing efficient technologies for lithium extraction from Salt Lake brines. Li 1.6 Mn 1.6 O 4 spinel shows high lithium selectivity and notable theoretical uptake capacity, indicating strong application potential in lithium extraction. However, the industrial application of this material is limited by its strong Jahn-Teller effect and manganese dissolution loss. In this study, LiOH and MnCO 3 were selected as the raw materials and La 2 O 3 was used as the doping modifier. The La 3+ -doped Li 1.6 Mn 1.6 O 4 precursor (La-LMO) was fabricated through hydrothermal and high-temperature solid-phase synthesis techniques. Then La 3+ doped H 1.6 Mn 1.6 O 4 lithium ion-sieve (La-HMO) was prepared by pickling. The materials' structure and morphology were examined using XRD, SEM, TEM, and XPS techniques. La 3+ doping does not alter the spinel structure of LMO but reduces Mn 3+ content, mitigates the Jahn-Teller effect, lowers the manganese dissolution rate, and enhances structural stability. Adsorption of Li + onto La-HMO follows pseudo-second-order kinetics and fits the Langmuir model, suggesting homogeneous monolayer adsorption driven by chemisorption. In the lithium extraction experiment from the brine of West Tai Kinel Salt Lake, La-HMO demonstrated high adsorption capacity and superior selectivity for Li + . After five cycles, La-HMO maintained an adsorption capacity of 33.10 mg/g, higher than the 26.80 mg/g for undoped HMO. The manganese dissolution rate dropped from 4.65% to 4.04%. The study significantly improved the adsorption properties and structural stability of HMO by doping La 3+ , which has broad application prospects in the separation and extraction of lithium resources in Salt Lake.
研究领域:
材料科学
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化学工程
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无机化学
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环境科学
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能源技术
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Aihong Shi,Zixiang Guo,Jin Long,Yue Liu,Wenge Jiang
Lithium ion sieve Li 1.6 Mn 1.6 O 4 (LMO) is a promising adsorbent for lithium extraction from liquid resources due to its high Li + selectivity and theoretical adsorption capacity. However, its practical application is limited by poor structural stability and the decrease of adsorption capacity resulting from gradual Mn dissolution loss during acidic regeneration process. Herein, a surface modification strategy was proposed to construct a continuous and dense CeO 2 coating on LMO surface, effectively addressing the critical challenge of structural instability and simultaneously improving adsorption performance. This protective layer suppressed Mn leaching, reducing the leaching rate to 3.33% in the first cycle compared with 4.57% for pristine LMO, and further to below 3% after ten consecutive adsorption-desorption cycles, effectively enhancing the structural stability. Furthermore, the excellent hydrophilicity of the CeO 2 coating could enhance the effective contact between the Li + ions in solution and the adsorbent, promoting the migration of Li + and its exchange with protons. As a result, the lithium uptake of optimized CeO 2 -coated LMO composite (CeO 2 @LMO) was 32.55 mg·g −1 much higher than 27.92 mg·g −1 in bare LMO, while retaining 85.50% of its initial capacity after ten cycles. Simulation results further revealed that CeO 2 @LMO exhibited a lower adsorption energy ( E ad ) and a reduced Li + diffusion energy barrier compared with LMO, facilitating Li + migration from the aqueous phase to the solid-liquid interface and accelerating its diffusion within the adsorbent. This work demonstrates that a single surface modification can simultaneously overcome LMO's key limitations, offering a viable strategy for developing durable and efficient lithium recovery systems.
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产品关联
DOI
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2020
·
IF 2.726
Guotai Zhang,Jingze Zhang,Yuan Zhou,Guicai Qi,Jinbo Zeng,Yanxia Sun,Yue Shen,Xiang Li,Xiufeng Ren,Shengde Dong,Chao Sun,Zhaowei Wu,Chunxi Hai,Weiping Tang
Solid-phase reactions were used for the synthetization of the spinel Li 1.6 Mn 1.6 O 4 powder and the lithium ion-sieve MnO 2 ·0.5H 2 O was subsequently obtained by the leaching of the lithium. The physical characterization showed that the polycrystalline precursor and the MnO 2 ·0.5H 2 O were nearly pure spinel, as well as that during the process of the adsorption-desorption, the structural stability was high. The Langmuir isotherm and pseudo second-order kinetics model showed consistency with the adsorption behavior , which indicated the presence of homogeneous adsorption sites for the lithium adsorption and that its process was chemisorption . Adsorbents were found to remain being characterized with a relatively high Li + uptake (26.13 mg g −1 ) with low manganese extracted (1.71%) after the circulation experiment was performed up to 5 times, proving a significant repeatability and stability for the lithium ion-sieve. The concentration factors exhibited the highly selective adsorption capacity for absorbent from Qarhan raw brine with high concentrations of Na + , K + , Ca 2+ , Mg 2+ . The adsorbents could be efficiently used for Li + recovery from Salt Lake brine as well as its excellent potential for further application.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
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2022
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IF 11.211
Lu-Ri Bao,Jing-Ze Zhang,Wei-Ping Tang,Shu-Ying Sun
The Mn-based Li 1.6 Mn 1.6 O 4 ion sieve is among the most effective lithium adsorbents due to its high lithium-ion adsorption capacity and selectivity for Li-ions. However, the inherent disadvantages of manganese dissolution and low structural stability prevent its industrial application. In this study, a series of Li 1.6 Mn 1.6 O 4 @R were synthesized by the low temperature solid phase hydrothermal method that exhibit highly anti-dissolution properties for the lithium adsorption from brine water. The LMO-L, LMO-LM, and LMO-M adsorbents show great adsorption capacities of 46.0 mg g −1 , 43.0 mg g −1 , and 38.0 mg g −1 compared to the 42.3 mg g −1 for the pristine adsorbent. After 20 cycles the dissolution loss of Mn was 0.06 % of LMO-L adsorbents. This improvement in adsorption properties is attributed to the stabilized layered structure due to the evolution of oxygen during the coating reaction, and the inhibition of the interfacial side reactions between the solution and the adsorbent by metal oxide coating. X-ray diffraction, and X-ray photoelectron spectroscopy analysis indicate the formation of Li 2 MnO 3 on the material surface, which can increase tetravalent manganese on the surface. Furthermore, our work may provide new insights for the design of efficient Mn-based adsorbents with high stability for water treatment applications.
研究领域:
材料科学
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环境科学
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化学工程
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无机化学
✓ 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）