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![Fig. 2. Map of global distribution for lithium resources [5].](publication/340030643/figure/fig2/AS:870780829175814@1584621736863/Map-of-global-distribution-for-lithium-resources-5_Q320.jpg)
With the large-scale use of lithium-ion batteries, the global demand for lithium resources has increased dramatically. It is essential to extract lithium resources from liquid lithium sources such as brine and seawater, as well as recycled waste lithium-ion batteries. Among various liquid lithium extraction technologies, lithium ion-sieve (LIS) ads...
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... this review, we summarize the chemical structure and adsorption mechanism of different LMO-type LIS. Emphasis is placed on preparation methods of LMO precursors and forming technologies for powder adsorbent (e.g., granulation, membrane formation, and foaming), followed with some prospects regarding LMO-type LIS (see Fig. ...
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... time due to its unique heating mechanism. Chitrakar et al. [49] achieved semi-crystalline orthorhombic LiMnO 2 by microwave hydrothermal using γ-MnOOH and LiOH at 120 °C. The reaction time was only 30 min, which was significantly reduced compared with the traditional hydrothermal day. Moreover, the sample obtained in this process is needle-like (Fig. 10a), which is different from the cubic shape (Fig. 10b) obtained by conventional hydrothermal method at the same temperature. It suggested that a direct interaction between γ-MnOOH and the microwaves, in addition to the rapid heating of the LiOH solution. ...
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... et al. [49] achieved semi-crystalline orthorhombic LiMnO 2 by microwave hydrothermal using γ-MnOOH and LiOH at 120 °C. The reaction time was only 30 min, which was significantly reduced compared with the traditional hydrothermal day. Moreover, the sample obtained in this process is needle-like (Fig. 10a), which is different from the cubic shape (Fig. 10b) obtained by conventional hydrothermal method at the same temperature. It suggested that a direct interaction between γ-MnOOH and the microwaves, in addition to the rapid heating of the LiOH solution. ...
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... obtained particles are fine, narrowly distributed, and well crystallized, as shown in Fig. 11. Naghash and Lee [56] prepared LiMn 2 O 4 by co-precipitation method. In this process, stearic acid in tetramethylammonium hydroxide (TMAH) is used to co-precipitate lithium and manganese in stoichiometric proportions from MnSO 4 and LiNO 3 solutions. Sinha et al. [57] prepared submicron size particles of LiMn 2 O 4 by the ...
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... et al. [9] prepared Li 1.67 Mn 1.67 O 4 by heating o-LiMnO 2 at 450 °C in air. They proposed that the particle shape became clear with heating, but particle growth by calcination did not take place. In this process, the DTA-TG curves of o-LiMnO 2 (Fig. 12) showed an 8.5% weight gain, which agrees well with the theoretical weight increase by ...
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... divalent metals are the most studied elements in doping modifications. Feng et al. [61] studied the Li + extraction reactions in LiZn 0.5 Mn 1.5 O 4 spinel. They found that the Li + extraction and insertion proceeded by ion-exchange type mechanisms. The structure of this metal-doping material is shown in Fig. 13. Chitrakar et al. [62] first prepared spinel-type lithium antimony manganese oxide by aging the precipitates that were obtained by reaction of a mixed aqueous solution of manganese(II) and antimony(V) chlorides with (LiOH + H 2 O 2 ) solution, followed by hydrothermal treatment at 120 °C. The results showed that the exchange capacity ...
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... the other hand, their research group also obtained granulated polyacrylamide (PAM)-MnO 2 ion-sieve with 0.3-0.7 mm diameter by the inverse suspension polymerization method using Li 4 Mn 5 O 12 as the precursor, acrylamide as the binder, N,N'-methylenebisacrylamide (MBA) as the cross-linker, and ammonium persulfate (APS) as the initiator (Fig. 14) 20 . The experiment showed that the maximum lithium equilibrium adsorption capacity is up to 2.68 mmol g -1 at 303 K. Furthermore, in the packed column, the Li + loading amount of PAM-MnO 2 ion-sieve remained almost constant after the 30 cyclic adsorption-desorption experiments (see Fig. ...
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... and ammonium persulfate (APS) as the initiator (Fig. 14) 20 . The experiment showed that the maximum lithium equilibrium adsorption capacity is up to 2.68 mmol g -1 at 303 K. Furthermore, in the packed column, the Li + loading amount of PAM-MnO 2 ion-sieve remained almost constant after the 30 cyclic adsorption-desorption experiments (see Fig. ...
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... of 10 wt% PVC and 15 wt% Li 1.67 Mn 1.67 O 4 in DMAc and liquid film thickness of 0.30 mm is optimum for adsorption. The adsorption cycle experiment indicated that this membrane-type adsorbent could be effectively regenerated and reused for lithium enrichment without significant adsorption capability loss. The process diagram is shown in Fig. ...
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... et al. [73] prepared an LMO-foam by a polyurethane template method using the oxygen-containing pitch as the support and crosslink. The result showed that the foam-type adsorbent had a homogeneous three-dimensionally interpenetrating network. SEM images of LMO foam are shown in Fig. 17. It exhibited considerable lithium adsorption capacities of 1.49 mg g -1 in brine. This makes the LMO-foam a promising inorganic lithium adsorbent. However, the combination of the pitch support and the nano-particles became loose after several adsorption cycles, and the numerous environmentally hazardous substances generated in the ...
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... [74] obtained millimeter-sized spherical ion-sieve foams (SIFs) from LMO by a composite process of foaming, drop-in-oil, and agar gelation. The experimental results showed that the prepared SIFs possessed a hierarchical trimodal pore structure after acid treatment. SEM images of the cross-sectional area (inner surface) of the SIFs are shown in Fig. 18. The maximum lithium adsorption capacities of the adsorbent could reach 3.4 mg g -1 in seawater. Moreover, after five adsorption cycles, the lithium uptake amount remained over 95%. It suggested that the foam-type LMO could be a promising candidate as an environmentally friendly and semi-permanent lithium ...
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... fabricated a flexible LMO/PVA composite foam with hierarchical porosity composed of macro and mesopores by a devised method of combined surfactant blending, cryo-desiccation and chemical cross-linking. The corresponding preparation schematic diagram of this material is shown in Fig. 19. In this work, PVA acted as binder and support; this accessible material with high hydrophilicity improved the kinetic properties of composite foam adsorbent. Compared with the corresponding powder, the LIS/PVA foams produced minimal reductions in Li + capacity due to its high porosity, excellent surface area, and superior LMO loading ...
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... package method is an interesting LMO forming method proposed by Chung et al. [80] The schematic diagram is shown in Fig. 21. In this method, the inorganic adsorbent powder was wrapped in PSF/non-woven fabric composite membrane to form a "tea bag". The proposed system has the advantage of direct application in the sea without using pressurized flow system. Thus, they indicated that it could be the most promising system for lithium uptake from seawater. ...
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... The redox mechanism was proposed by Hunter (Ding et al., 2020). Taking LiMn 2 O 4 as an example, the adsorption/desorption mechanism of Li + can be explained by the redox mechanism when the precursor of ion sieve is acid washed. ...
As a crucial component of modern energy, lithium is becoming ever more vital. As a result, lithium-ion-containing wastewater is being created in huge quantities, causing resource loss and environmental damage that must be effectively treated. Adsorption techniques are popular for lithium extraction and recovery due to their benefits of low energy usage, straightforward procedures and excellent recycling. The lithium-ion sieves (LISs) adsorption technique, which has the qualities of high lithium selectivity and adsorption capacity, low energy consumption, environmental protection and safety, is now regarded as the most promising lithium extraction technology. LISs composite forming technology (such as granulation, foaming, fiber forming, film forming and magnetization) and the adsorption technique, specifically the LISs adsorption mechanism, are discussed in this review. The effectiveness of extracting lithium from lithium-containing solutions using LISs adsorbents is reviewed and the difficulties of recovering lithium resources by LISs are presented, thereby offering a guide for their use in treating wastewater containing lithium.
... Subsequently, lithium ions from the aqueous solution can preferentially occupy the created vacancies, whereas other coexisting ions such as Na + , K + , Ca 2+ , and Mg 2+ face resistance due to steric effects. Finally, after selective lithium adsorption, [LIS(H)] is transformed into [LIS (Li)], completing the process known as the LISs effect (Xu et al., 2016;Weng et al., 2020). ...
The escalating demand for lithium in electrochemical energy advice has stimulated growing focus on extracting Li from alternative sources such as brines. Lithium ion-sieves (LISs), comprising manganese-based and titanium-based LISs, emerging as a promising Li recovery technique, attributed to their exceptional capacity for lithium uptake, selectivity, and recyclability. However, practical implementation faces two critical challenges: the potential dissolution of specific ions (e.g., Mn3+ and Ti4+) and the severe particle aggregation during synthesis. In addition, coexisting ions like Mg2+ hinder the selective adsorption of Li+ due to their similar chemical properties. To meet these challenges, heteroatom doping is supposed to enhance the performance of LISs and diverse heteroatom doped LISs have been developed recently. Herein, this comprehensive review begins by delving into the fundamental aspects of LISs, including the LIS effect and types of LISs. Subsequently, adsorption behavior and practical application of modified LISs were discussed. Finally, prospects and research directions to solidify the role of LISs in pioneering environmentally friendly and economically viable lithium recovery methods are outlined.
... This high demand, along with the massive natural reserves of Li, suggest that there is a dire need for the development of facile and feasible technologies for its recovery. 3 ...
... Granulation of metal-based LISs using biopolymer binding agents has been reported [3,6,24,29] to produce particles with engineered properties such as mechanical strength, porosity, bulk density, and particle size distribution for tailored applications [26,30]. The use of binding agents (e.g., biopolymers, synthetic organic polymers, and inorganic materials) afford LISs that can be easily isolated from the aqueous media, thus enhancing their utility in large scale industrial application. ...
... LiSbO3, LiAlMnO4 and LiNbO3 [31,32]. The reader is referred to an amplitude of references that have reported on the various types of LISs and their preparation strategies [3,6]. The focus in this section is to provide a general strategy for the preparation of LISs. ...
The high demand for lithium (Li) relates to clean renewable storage devices and the advent of electric vehicles (EVs). The extraction of Li ions from aqueous media calls for efficient adsorbent materials with various characteristics, such as good adsorption capacity, good selectivity, easy isolation of the Li-loaded adsorbent, and good recovery of the adsorbed Li ions. The widespread use of metal-based adsorbent materials for Li ions extraction relates to various factors: (i) the ease of preparation via inexpensive and facile templation techniques, (ii) excellent selectivity for Li ions in a matrix, (iii) high recovery of the adsorbed ions, and (iv) good cycling performance of the adsorbents. However, the use of nano-sized metal-based LISs is limited due to challenges associated with isolating the loaded adsorbent material from the aqueous media. Adsorbent granulation process employing various binding agents (e.g., biopolymers, synthetic polymers, and inorganic materials) affords functional particles with modified morphological and surface properties that support easy isolation from the aqueous phase upon adsorption of Li ions. Biomaterials (e.g., chitosan, cellulose, alginate, and agar) are of particular interest because their structural diversity renders them amenable to coordination interactions with metal-based LISs to form 3D microcapsules. The current review highlights recent progress in the use of biopolymer binding agents for the granulation of metal-based LISs, along with various crosslinking strategies employed to improve the mechanical stability of the granules. The study reviews the effects of granulation and crosslinking on adsorption capacity, selectivity, isolation, recovery, cycling performance and the stability of the LISs. Adsorbent granulation using biopolymer binders has been reported to modify the uptake properties of the bio-adsorbent materials to varying degrees, in accordance with the surface and textural properties of the binding agent. The review further highlights the importance of granulation and crosslinking for improving the extraction process of Li ions from aqueous media. This review contributes to manifold areas related to industrial application of LISs, as follows: 1) to highlight recent progress in the granulation and crosslinking of metal-based adsorbents for Li ions recovery, 2) to highlight the advantages, challenges, and knowledge gaps of using biopolymer-based binders for granulation of LISs, and finally, 3) to catalyze further research interest into the use of biopolymer binders and various crosslinking strategies to engineer functional adsorbent materials for application in Li extraction industry. Properly engineered extractants for Li ions are expected to offer various cost benefits in terms of capital expenditure, percent Li recovery, and reduced environmental footprint.
... Lithium is absorbed and extracted from the complicated aqueous solutions using Liion sieves, which are high-ion filtering selective adsorbents [57][58][59]. Lithium-ion sieves (LMO and LTO) based on manganese oxide and titanium oxide are distinguished due to their high adsorption capacity [60] and regarded as better promising technologies for lithium extraction from solutions due to the less power consumption and environmental safety [61]. ...
... The spinel LiMn2O4 has a 1:2 ratio of Li to Mn cations but this ratio can occasionally be exceeded [64]. However, lithium adsorption during recycling and manganese dissolution during processing both affect the stability structure of spinel [61]. The efficiency of substance absorption is greatly influenced by the shape, porosity and crystal structure of adsorbent material [57,65]. ...
An increasing number of electric vehicles, hybrids, and synergistic types are adding electronic components, driving up demand for
lithium and its derivatives. These chemicals comprise 80% of the worldwide market and come in forms such as carbonate, lithium hydroxide
and mineral concentrates. The use of lithium is predicted to surge by 60% in the coming years due to the proliferation of electric vehicles.
This demands efficient and rapid deposit detection methods as well as economical and high-resolution exploration equipment. The
quantity and geographical distribution of fossil and ore mineral deposits can be easily mapped using hyperspectral photography. Since
salt lakes, oceans, and geothermal water hold the majority of the world’s lithium reserves ranging from 70% to 80%, these areas are ideal
for the lithium extraction process. In this regard, there is an increase in research targeted at industrial lithium production from water
resources. Recycling lithium-ion batteries is an alternative method that can be utilized to increase the production of lithium. Geothermal
waters have lower lithium contents than brines and some of the processes are not suitable. Evaporation methods, solvent extraction,
membrane technology, nanofiltration and adsorption can all be used to extract lithium from liquid media. Thus, lithium extraction from
aqueous solutions was the focus of this review article, which aimed to provide straightforward technical solutions, low costs, decreased
environmental impact and excellent selectivity for the lithium industry.
... At present, lithium resources mainly exist in the form of solid lithium ore and liquid lithium resources in salt lake brine. Lithium extracted from salt lake brine accounts for 75% of the world's lithium production [14][15][16] and involves lower energy consumption and costs than those of ore lithium. With the increasing demand for lithium resources, the exploration of lithium in deep underground brines in petroliferous basins has attracted increasing attention [17][18][19][20]. ...
There are considerable reserves of low-grade solid potash resources in the shallow part of Mahai Salt Lake in the Qaidam Basin, and the lithium brine resources resulting from solid–liquid conversion and mining are quite abundant. The comprehensive utilization of these resources is an important and urgent problem. In this study, to fully utilize these resources, the shallow low-grade solid potash ore in Mahai Salt Lake was used for systematic simulated ore dissolution experiments, combined with geochemical and X-ray diffraction analyses. The following key results were obtained: (1) Most Li+ in the Mahai mining area was deposited on the soluble salt minerals in silt or clay, and the appropriate concentration of solvent can help to dissolve more Li+ and K+; (2) the saturation time of Li+ was longer than that of K+. Therefore, the dissolution time for the mine can be appropriately extended during the production process to dissolve more Li+; (3) the solid–liquid conversion aqueous solution mining method can separate the lithium part of clay deposits and is associated with salt rock in the brine, which is a potential lithium resource. These experimental results provide a theoretical basis for salt pan production.
... The higher Li/Mn ratio, the higher the theoretical adsorption capacity. Since Li/Mn is 1, MnO 2 ⋅0.5H 2 O has the highest theoretical adsorption capacity (Weng et al., 2020). At present, the adsorbents are mainly prepared in the form of powder, which has problems of poor permeability and difficult recycling. ...
With the increasing application of the industrialization of lithium and its derivatives, there has been a surge of interest in recovering this resource from liquid sources. However, synthesizing adsorbents with industrial significance is still a significant challenge. Herein, the precursor Li1.6Mn1.6O4 of H1.6Mn1.6O4 powder absorbent with the highest theoretical adsorption capacity and the lowest Mn dissolution loss rate was first synthesized by hydrothermal or high-temperature solid phase method. The commercialized wet spinning apparatus, which has convenient operation and a simple process, was used to prepare PVDF/HMO spinning fiber to recover lithium resources from geothermal water. It has a large specific surface area of 31.45 m2 g−1 and a pore size of 9.04 nm, and the adsorption capacity was 14.95 mg g−1, with the distribution coefficient of Li+ being 1404.96 mL g−1. Furthermore, the equilibrium was reached within just 2 h at pH 12, and the elution time was just 1 h. Even after the fifth cycle, the adsorption capacity remained high at 14.21 mg g−1. These characteristics indicate that the new material has excellent application potential for lithium recovery from geothermal water.
... These processes determine the third type of lithium deposits -sedimentary. In them, lithium is concentrated mainly in the brine of salt lakes (Weng et al., 2020;Rafael 2021;Abdullah et al., 2022;Yuecheng et al., 2022). ...
The visual-polythermal approach was used to investigate the solubility of the LiNO3-NH4Cl-H2O nitrate system's constituents over a wide range of temperatures and concentrations. Internal incisions were used to study the system, and as a result, the system's polythermal solubility diagram was produced. The phase diagram delimits the crystallization fields of ice, LiNO3·2H2O, LiNO3, NH4Cl, and the new phase LiCl·3H2O, NH4NO3. The formation of a new compound was confirmed by the methods of chemical and physicochemical analysis. This system's features and composition are shown. It can provide a scientific foundation for the extraction of lithium compounds from water sources based on the knowledge learned about the solubility of the components in the system under study.
... [22][23]. To obtain Li2TiO3 and Li4Ti5O12 oxides, various synthesis methods are used: "in situ" hydrolysis [24], solid-phase, hydrothermal [25], and sol-gel synthesis [26]. The significant disadvantages of these methods include the difficulty of controlling the chemical composition and parameters of the crystal structure, textural characteristics and morphology of the obtained oxides. ...
... Second, the lithium adsorbent substance must exhibit a strong predilection for lithium and have a high adsorption capacity to enable effective extraction from complicated, highly salinized brine deposits. Ion exchange resin [101], aluminum adsorbent [102], manganese adsorbent [103], and titanium adsorbent [104] are all exceptional adsorbents for lithium adsorption. Liu et.al. ...
The global demand for lithium, which is indispensable for electric cars and electrical devices, has increased. Lithium recovery from oilfield-produced water is necessary to meet the growing need for lithium-ion batteries, protect the environment, optimize resource utilization, and cut costs to ensure a successful energy transition. It is useful for keeping water supplies in good condition, adhering to legal requirements, and making the most of technological advances. Oil and gas companies might see an increase in revenue gained through the lithium extraction from generated water due to the recouping of energy costs. Therefore, this review focuses on contamination and treatment strategies for the oilfield-produced water. It includes a discussion of the global lithium trade, a financial analysis of lithium extraction, and a comparison of the various methods currently in use for lithium extraction. It was evaluated that economic considerations should be given priority when selecting environmentally friendly methods for lithium recovery from oilfield-produced water, and hybrid methods, such as adsorption–precipitation systems, may show promising results in this regard. Lastly, future prospects for the lithium industry were also discussed.
... The adsorption method uses lithium-selective adsorbents to extract lithium from polyionic water sources and then desorb them with other solvents to extract lithium. The main adsorbent requirements include sufficient capacity for adsorption, adequate performance stability and high Li selectivity [52]. ...
Lithium compounds (carbonate, chloride) are the most widely used materials in glass, ceramics, pharmaceuticals, and electric vehicle batteries. The production of vehicles runs on electricity, and some of the devices having electronic circuits gradually increased the Li demand for the derivatives. The material base is mainly focused on Li production and Li derivatives. Lithium reserves account for 70-80% of Salt Lake waters; marine and geothermal waters account for the total lithium reserves and can be used as the best raw material for Li extraction. Many ways of extracting Li have been investigated using water resources. The adsorption method is the most effective method among those. This article provides information about some sorbents which is used in the process of Li extraction by adsorption method, their merits and demerits, as well as their impact on the environment. The use of the efficient and most promising selective type of sorbents with higher functionality, lower energy consumption, and environmental safety ensures the achievement of high economic performance.
