Selective Recovery Of Lithium Research Articles

LiNi0.5Mn1.5O4-based hybrid capacitive deionization for highly selective adsorption of lithium from brine

In recent years, the demands for lithium are increasing sharply with the fast development of electrical vehicles, new green energy and portable electronic devices. To meet the demands, selective recovery of lithium from brine/seawater has attracted extensive attention. LiMn2O4 (LMO) is a good redox material for lithium recovery. However, the dissolution of Mn is inevitable during the redox process which can lead to severe capacity decay and poor cycle performance. In this paper, LiNi0.5Mn1.5O4 (LNMO) nanoparticles were prepared through one-step solid-state sintering and applied as a positive electrode in the hybrid capacitive deionization cell for lithium recovery. Cyclic voltammetry (CV) scan of the LNMO electrode in LiCl aqueous solution presented clear redox peaks, illustrating the reversible intercalation/de-intercalation of Li+ into/from LNMO; while the Na+, K+, Mg2+ and Ca2+ cations had negligible intercalation. Combined with an activated carbon (AC) negative electrode, the hybrid capacitive deionization cell (LNMO||AC) was assembled to selectively adsorb lithium, arriving at the adsorption amount of ~260 µmol/g, almost three times higher than that of the symmetric AC cell (AC||AC). Even in the Mg2+ and Li+ mixed binary salt solution at a high CMg2+/CLi+ ratio of 30, LNMO remained high selectivity to Li+ with the separation factor of ~104 achieved. In the synthetic brine water containing various salts, the LNMO||AC cell kept excellent selectivity to Li+ with the adsorption amount still remaining ~230 µmol/g. And the cell can preserve a retention of ~86% after 100 cycles, much higher than the LMO||AC cell (~50%). Meanwhile, neither Mn2+ nor Ni2+ were found in the cycling solution of LNMO||AC cell. Nevertheless, the LMO||AC cell deteriorated gradually with the dissolution loss ratio of Mn in LMO close to 40%. Such excellent selectivity and high stability of LNMO enable it applicable for practical lithium recovery application, superior to LMO.

Tailoring hydrophobic deep eutectic solvent for selective lithium recovery from the mother liquor of Li2CO3

• HDES synthesized by oleic acid and tetrabutyl ammonium chloride are more environmentally benign co-extractant. • The green synergic system TBP-HDES showed high lithium selectivity extraction. • The extraction mechanism were mainly cation exchange and Li + coordination. Recovering Li + from the mother liquor obtained during the process of Li 2 CO 3 production has been considered as a promising solution to the shortage of lithium resources. However, as the mother liquor is a complex saline system with high concentration of Li + (1.42 g/L) and a large amount of Na + (55.62 g/L), there is no competent method to carry out for the effective utilization of Li + . This work reports a class of hydrophobic deep eutectic solvents (HDESs) formed by tetrabutylammonium chloride (TBAC) and oleic acid (OA), which is a novel co-extraction reagent for Li + extraction. In addition, tributyl phosphate (TBP) is used as extractant and ammonia is applied to regulate pH. TBAC/3OA showed the highest extraction efficiency in single extraction (76.8%) with the ammonia concentration, the volume ratio of organic phase and aqueous phase (O/A phase ratio), and volume fraction of HDES as 1.5 mol/L, 1, and 30%, respectively. Mechanism studies through the UV–vis and FT-IR proved that cation exchange between Li + and HDES, and Li + coordination was the dominant force in the separation process. The complexing ability of P = O in TBP led to the selective extraction of Li + . The reusability experiments of organic phase demonstrated that the extraction efficiency was still above 60% after five cycles, indicating the favorable stability of the extraction system. Finally, the separation factor ( β Li/Na ) of Li/Na in the mother liquor was 20.5, indicating that the TBP-HDES system has the capability to selectively extract Li + with high Na/Li ratio. This will help to design possible green HDES for lithium recovery.

Sulfonated poly (ether ether ketone) composite cation exchange membrane for selective recovery of lithium by electrodialysis

Lithium is in demand since decades due to high applicability in batteries for electronic devices, which is expected to increase by 8 to 11% every year and Lithium ion battery market is estimated to grow to € 180 billion by 2024. Land deposits and seawater are two major sources of lithium but availability in sea water is higher than land. So an efficient technology is required to recover the lithium from sea water. Electrodialysis (ED) may be an alternate approach to recover the lithium from sea by selective ion exchange membranes. Here, Lithium selective ion exchange membranes have been synthesized by modification of sulfonated poly (ether ether ketone) (SPEEK) with lithium selective nanomaterial. Synthesized membranes were characterized for their chemical, structural and morphological structures and uniform dispersion of lithium selective nanomaterials. Composite membrane shows better lithium exchange capacity with excellent lithium conductivity as compared to SPEEK membrane. The adsorption of lithium (15.2 mg/g) found to be five times higher than that of Mg while recovery of lithium was 64% using electrodialysis process by NC-4 composite membrane. Selectivity factor for composite membrane were 4.82, 3.0 and 2.17 for Li/Mg, Li/K and Li/Na, respectively. The selective composite membranes can be suitable for Li-ion recovery from sea brine/bittern on large scale.

Understanding the Behaviors of λ-MnO2 in Electrochemical Lithium Recovery: Key Limiting Factors and a Route to the Enhanced Performance.

Recently developed electrochemical lithium recovery systems, whose operation principle mimics that of lithium-ion battery, enable selective recovery of lithium from source waters with a wide range of lithium ions (Li+) concentrations; however, physicochemical behaviors of the key component-Li+-selective electrode-in realistic operation conditions have been poorly understood. Herein, we report an investigation on a λ-MnO2 electrode during the electrochemical lithium recovery process with regards to the Li+ concentration in source water and operation rate of the system. Three distinctive stages of λ-MnO2 originating from different limiting factors for lithium recovery are defined with regard to the rate of Li+ supply from the electrolyte: depleted, transition, and saturated regions. By characterization of λ-MnO2 at different stages using diverse X-ray techniques, the importance of Li+ concentration in the vicinity of the electrode surface is revealed. On the basis of this understanding, increasing the density of the electrode/electrolyte interface is suggested as a realistic and general route to enhance the overall lithium recovery performance and is experimentally corroborated at a wide range of operation environments.

Selective recovery of lithium and iron phosphate/carbon from spent lithium iron phosphate cathode material by anionic membrane slurry electrolysis

A simple, green and effective method, which combined lithium iron phosphate battery charging mechanism and slurry electrolysis process, is proposed for recycling spent lithium iron phosphate. Li and FePO4 can be separation in anionic membrane slurry electrolysis without the addition of chemical reagent. The leaching efficiency of Li can reach to 98% and over 96% of Fe are recycled as FePO4/C. Kinetics analysis indicates that the surface chemical reaction is the control step during the slurry electrolysis. Additionally, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Electrochemical Impedance Spectroscopy (EIS) characterization and thermodynamic analysis are employed to investigate the leaching mechanism. It is found that the spent LiFePO4 is delithiated and oxidized to FePO4 by the function of e−, which is similar as the LiFePO4 battery charging process. EIS analysis also verify the kinetics results, the charge transfer resistance controlled the leaching process. Finally, a novel process for recovery of spent LiFePO4 is proposed. The recovered Li2CO3 and FePO4/C can be used for resynthesize LiFePO4, and the resynthesized LiFePO4 exhibits reversible capacities of 143.6 mAh g−1 at 1C and high current efficiency, stable cycle performances at 0.1 and 0.5C which meets the basic requirements for reuse.

Selective Recovery of Lithium from Spent Lithium-Ion Batteries by Coupling Advanced Oxidation Processes and Chemical Leaching Processes

Traditional technologies for the recycling of spent lithium-ion batteries (LIBs) mainly focus on reductive leaching, which often leads to total leaching rather than selective leaching of metals. As...

Selective recovery of lithium from geothermal water by EGDE cross-linked spherical CTS/LMO

As a new-type liquid lithium resource, the recovery of lithium from geothermal water is of great significance due to the increasing importance of lithium in modern industry. In this work, different lithium manganese oxides (LMOs), including LiMn2O4, Li1.66Mn1.66O4, and Li4Mn5O12, were synthesized and applied for selective recovery of lithium from geothermal water. It was found that the powdery Li4Mn5O12 exhibits high performances for low concentrations of Li+ and was then successfully granulated using chitosan (CTS) at a mass ratio of CTS/LMO = 3:2. The hydrophily of CTS leaded to a serious dissolution loss of CTS/LMO under acidic conditions, but it was successfully solved by direct cross-link of the spherical material using ethylene glycol diglycidyl ether (EGDE), by which the dissolution loss in 0.25 mol/L HCl was decreased from 27.65% to no more than 0.6%. The equilibrium adsorption capacity of Li+ in geothermal water reached 8.98 mg/g at 303.15 K, while the attenuation of adsorption capacity was no more than 1.1% after five times adsorption-desorption cycles. The separation factors between Li+ and other ions were all higher than 51 with a distribution coefficient of Li+ reaching up to 1113.27 mL/g. All these properties demonstrate that the developed material has high selectivity and stability, and can be used as a candidate for selective recovery of lithium from geothermal water or other solutions.

Highly selective lithium recovery from high Mg/Li ratio brines

Here, we report a new liquid-membrane electrodialysis capable of selectively recovering lithium from high Mg/Li ratio brines. The liquid membrane is composed of an ionic liquid system as the Li+ carrier that presents high selectivity toward Li+ and long-term sustainability, and 2 solid cation-exchange membranes to sandwich the carrier. Recognition and selective electromigration of Li+ can be achieved by the sandwiched liquid membrane assisted by an electric field. The Mg/Li decreases from 50:1 in the initial feeding brine to 0.5:1 in the receiving solution after electrodialysis at a current density of 4.375 A·m−2 for 12 h. Moreover, higher current efficiency (65%) and lower specific energy consumption (16 Wh·g−1 Li) are obtained compared to typical electrodialysis processes. From the perspective of practical application, the Mg/Li drops to 0.26:1 from 53:1 in the old brine from West Taijinair, and K+ and Ca2+ in the brine are almost completely blocked by the liquid membrane. This method displays a great perspective on the application for lithium recovery from high Mg/Li brines owing to its high selectivity, efficient energy utilization, and environmental friendliness.

Porous lithium ion sieves nanofibers: General synthesis strategy and highly selective recovery of lithium from brine water

Lithium ion sieves (LIS) have gained great interest in lithium recovery. However, the synthesis of high stability, selectivity, and adsorption capacity of LIS is still a great challenge. Here, a general strategy combining electrospinning and calcination techniques is developed to fabricate a series of porous titanium-based LIS nanofibers. The porous structure created by calcination increases the exposure of the adsorption sites, which significantly accelerates the deintercalation and intercalation of Li+ from and into the vacancies in the framework. All of samples have good Li+ adsorption capacity and high selectivity for Li+. As a proof of concept, porous H4Ti5O12 nanofibers (P-HTO-NF) transformed from the electrospun porous Li4Ti5O12 nanofibers (P-LTO-NF) are systematically investigated in lithium recovery. P-HTO-NF possesses a superior adsorption capacity (59.1 mg/g), which is nearly close to the theoretical value (63.77 mg/g). The Freundlich isotherm model can well describe the adsorption isotherm data. The adsorption equilibrium can reach within 30 min (C0 = 300 mg/L, pH = 11, S/L = 60 mg/60 mL). The equilibrium distribution coefficient (Kd, mL/g) for Li + (232) is extremely higher than that for competing ions (1.41 for Na+, 1.17 for K+, 0.88 for Mg2+, 0.58 for Ca2+) (C0 = 40 mg/L for Li+, pH = 8), indicative of a highly selective recovery of lithium from brine water. The LIS show excellent stability with a low Ti dissolution and the adsorption capacity for Li+ remains 86.5% after 6 cycles. Our work provides a universal strategy for the synthesis of porous LIS.

Synthesis of Polyporous Ion-Sieve and Its Application for Selective Recovery of Lithium from Geothermal Water.

The widespread use of lithium-ion batteries has led to continuously increasing demands for lithium. In order to recover lithium from geothermal water, a novel composite lithium ion-sieve was synthesized and applied in this work. The stability of the material was successfully solved by granulating using acid-alkali resistant polyvinyl chloride as a binder, and its adsorption performances were also improved by using polyethylene glycol (PEG-6000) as a porogen to obtain a polyporous structure. When the developed material was applied for lithium separation from geothermal water, the adsorption capacity reached 12.84 mg/g at 328.15 K with an equilibrium time of about 12 h. The material can be well regenerated using 0.25 mol/L HCl to realize cycle use. The separation factors between Li+ and other co-existing ions were within the range of 273.58-521.28, and the attenuation of adsorption capacity after five cycles was no more than 2%. The high selectivity and reusability properties of the polyporous ion-sieve make the material a potential candidate for the selective separation and recovery of a low concentration of lithium from geothermal water.

Selective recovery of lithium from the Great Salt Lake using lithium manganese oxide-diatomaceous earth composite

Lithium is an important metal for energy storage applications. With the increase in demand for lithium in the near future it is important to explore low-grade brine resources, which contain the majority of known lithium resources. In this work, a λ-MnO2 diatomaceous earth composite adsorbent was synthesized by using a combination of hydrothermal treatment and solid-state calcination. The synthesized adsorbent was tested with LiCl buffered solution for various batch adsorption parameters. Loading of 28–29% λ-MnO2 on diatomaceous earth showed the best performance for lithium adsorption. The adsorption was found to follow the Langmuir isotherm model and pseudo second order kinetic model. The increase in adsorption capacity with higher temperatures indicates that lithium adsorption is endothermic in nature. It was also observed that there is a 30% loss in adsorption capacity after five adsorption-desorption cycles when hydrochloric acid was used as an eluent due to loss of Mn2+. Replacing hydrochloric acid with (NH4)2S2O8 as an eluent at 80 °C, increased the recycling stability of the adsorbent by decreasing manganese loss. The adsorbent was tested with Great Salt Lake water and 95% of lithium was extracted with high selectivity from the brine over alkali and alkaline earth metals.

Sustainable and Facile Method for the Selective Recovery of Lithium from Cathode Scrap of Spent LiFePO4 Batteries

Lithium recovery from spent LiFePO4 batteries is significant to prevent resource depletion and environmental pollution. In this study, the employment of “water in salt” electrolyte in LiFePO4 battery enlightened us to develop a novel method for the selective recovery of lithium from spent LiFePO4 batteries through oxidizing LiFePO4 to FePO4 with sodium persulfate (Na2S2O8). Effect of several variables on the Li leaching efficiency was investigated. Additionally, combined thermodynamic analysis and characterization of XRD, XPS were employed to investigate the leaching mechanism. More than 99% of Li can be selectively leached in 20 min at ambient temperature with only 0.05 times excess of Na2S2O8. The high leaching efficiency can be ascribed to the stability and without destruction for the solid structure during the oxidation leaching. A closed-loop process was then proposed for recycling entire spent LiFePO4 batteries, and finally high purity Li2CO3 (99 wt %) was successfully prepared. The process is econo...

Process Synthesis: Selective Recovery of Lithium from Lithium-Ion Battery Cathode Materials

A selective dissolution process to recover lithium from cathode materials by oxalic acid was investigated. The chemical reaction responsible for dissolution was identified, and the effects of opera...

Rapid and selective lithium recovery from desalination brine using an electrochemical system.

Due to the steep increase in the use of mobile electronics and electric vehicles, there has been a dramatic rise in the global lithium consumption. Although seawater is considered as an ideal future source of lithium, technological advances are necessary to ensure the economic feasibility of lithium recovery from seawater because the concentration and portion of Li+ are extremely low in seawater. Especially, battery-based electrochemical systems for lithium recovery have been considered as promising lithium recovery methods, though they have not been considered for seawater applications due to the extremely low concentration of Li+. In this study, we demonstrate that an electrochemical system based on a battery electrode material (λ-MnO2) can be used for efficient lithium recovery from desalination brine (2-3 times concentrated seawater). Our approach was able to capture Li+ within a substantially short period of time compared to conventional processes at a rate that was at least 3 times faster than that of adsorption processes, and our approach did not require acid or toxic chemicals unlike the other recovery technologies. Moreover, by consecutive operation of the system, a lithium recovery solution containing 190 mM of Li+ was obtained with only a small consumption of energy (3.07 Wh gLi-1), and the purity of Li+ was increased to 99.0%.

Selective Lithium Recovery from Seawater Using Crown Ether Resins

Selective Lithium Recovery from Seawater Using Crown Ether Resins

Recovery of valuable metals from mixed types of spent lithium ion batteries. Part II: Selective extraction of lithium

Extensive usage of different kinds of lithium ion batteries (LIBs) may result in a huge amount of complicated waste batteries stream, while insufficient attention has been paid on the selective recovery of lithium from these already complicated wastes. Herein, a novel approach was developed for the selective extraction of Li from mixed types of LIBs (LiCoO2, LiMn2O4, LiFePO4 and LiCo1/3Mn1/3Ni1/3O2) using mild phosphoric acid as efficient leaching agent. It can be concluded from leaching results that 100%, 92.86%, 97.57% and 98.94% Li can be selectively extracted from waste cathode materials of LiCoO2, LiMn2O4, LiFePO4 and LiCo1/3Mn1/3Ni1/3O2, respectively, while transition metals (Co, Mn, Fe and Ni) can be hardly leached in mild acidic media under optimized leaching conditions. In addition, high selectivity coefficients (βLi/Me) can be obtained during the extraction of Li from other metals. It can be also discovered from characterization results (SEM, XRD, FT-IR and Raman spectra) that leaching residues are phosphate precipitates, which might be used for the recycling of other metals and preparation of cathode materials. Results from leaching kinetics indicate that the leaching of Li is chemical and internal diffusion controlled reaction, with apparent activation energy (Ea) of 37.74, 21.16, 27.47 and 21.86 kJ/mol for LiCoO2, LiMn2O4, LiFePO4 and LiCo1/3Mn1/3Ni1/3O2, respectively. Finally, lithium phosphate with a purity of 98.4% can be obtained and the whole process can be efficient candidate for Li recovery with minor environmental impact and little waste produced.

Calix[4]arenes functionalized dual‐imprinted mesoporous film for the simultaneous selective recovery of lithium and rubidium

Calixarenes have been drawing tremendous interest due to their special structure, superior properties and numerous applications. In this work, a novel adsorbent material, calix[4]arenes functionalized dual‐imprinted mesoporous film (DIMFs) for the simultaneous selective recovery of Li(I) and Rb(I), was prepared via surface ionic imprinting. Compared with ordinary adsorbent materials, the synthesis process of the films used a cheap bio‐template and did not require extra steps but significantly enhances adsorption properties. The morphology and structure of prepared DIMFs were characterized by scanning electron microscopy, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT‐IR) and nitrogen adsorption–desorption measurements. Adsorption parameters (pH and temperature), adsorption kinetics and adsorption isotherms of the DIMFs were investigated by adsorption experiments. This novel adsorbent has inorganic–organic hybrid frameworks, high specific surface area and uniform pore size. The Langmuir and Freundlich isotherms, pseudo‐first‐order and pseudo‐second‐order kinetics of DIMFs were investigated; suggesting that the adsorption data well fits the Langmuir isotherm model, and the adsorption kinetics can be described by the pseudo‐second‐order kinetic model. In addition, dual‐imprinted mesoporous film exhibited superior selectivity for Li(I) and Rb(I). Cycle test demonstrated an outstanding of reusability, which appreciating their potential for industrial application.

Selective recovery of lithium from simulated brine using different organic synergist

Abstract The organic synergists, including Octanol, ethyl acetate (EA), butyl acetate (BA), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), N,N-bis(2-ethylhexyl) acetamide (N523) and 8-hydroxylquiolate, were added to the TBP–FeCl3 extraction system to extract lithium from brine. The effects of concentration of organic synergist and total organic extractant, molar ratio of Fe/Li, phase ratio, counter-current extraction and the acidity of stripping agent on lithium extraction were investigated to optimize the extraction conditions. Under the optimize conditions, the results of counter-current extraction showed the mixed extraction system was the preponderance on the lithium extraction. Especially the separation of lithium in organic phase and aqueous phase and the separation mass ratio of Mg/Li increased greatly. An extraction mechanism was proposed based on the analysis of FT-IR spectra and Raman spectra.

Selective recovery of lithium from spent lithium iron phosphate batteries: a sustainable process

An effective and sustainable approach is demonstrated for selective leaching of lithium from spent lithium iron phosphate batteries.

Fabrication of lithium ion imprinted hybrid membranes with antifouling performance for selective recovery of lithium

The LIHMs showed a distinctive adsorption capacity (27.10 mg g−1) and permselectivity (βK/Li = 5.3780, βCa/Li = 21.9402, βMg/Li = 15.5620) for Li+, which resulted from the effect of the special imprinted sites.