Lithium selective adsorption on low-dimensional titania nanoribbons

Mesoporous titania nanoribbons were synthesized via an optimized soft hydrothermal process and the derived titania ion-sieves with lithium selective adsorption property were accordingly prepared via a simple solid-phase reaction between Li₂CO₃ and TiO₂ nanomaterials followed by the acid treatment process to extract lithium from the Li₂TiO₃ ternary oxide precursors. First, mesoporous titania nanoribbons were prepared and the formation mechanism was discussed; second, the physical chemistry structure and texture were characterized by powder X-ray diffraction (XRD), (high-resolution) transmission electron microscopy (TEM/HRTEM), selected-area electron diffraction (SAED) and N₂ adsorption–desorption analysis (BET); third, the lithium selective adsorption properties were tested by the adsorption isotherm, adsorption kinetics measurement and demonstrated with the distribution coefficient of a series of alkaline and alkaline–earth metal ions.     

Adsorption behavior of Li+ onto nano-lithium ion sieve from hybrid magnesium/lithium manganese oxide

Magnesium (II) doped spinel lithium manganese oxide (LMS) was synthesized by soft chemical method and nanosized ion sieve manganese oxide (HMS) was prepared by extracting lithium and magnesium from LMS. The characteristics of HMS were studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, surface areas and determination of pH at the point of zero charge. Experiments were performed to study the effects of pH, adsorbent dose, contact time and Li⁺ concentration. The competitive model was used to describe the competition between Li⁺–H⁺ and the applicability of different kinetic models was evaluated. The results showed that the pH at the point of zero charge of HMS was about 7.8. The recycle of HMS explained that it could be used as Li⁺ adsorbent with topotactical extraction of lithium. Under optimized batch conditions up to 99.2% Li⁺ could be recovered from solution within 24 h. The adsorption process followed the pseudo-second-order model and followed an intraparticle diffusion model at the beginning.     

Li6V10O28, a novel cathode material for Li-ion battery

A novel cathode material, lithium decavanadate Li₆V₁₀O₂₈ with a large tunnel within the framework structure for lithium ion battery has been prepared by hydrothermal synthesis and annealing dehydration treatment. The structure and electrochemical properties of the sample have been investigated. The novel material shows good reversibility for Li⁺ insertion/extraction and long cycle life. High discharge capacity (132 mAh/g) is obtained at 0.2 mA/cm² discharge current and potential range between 2.0 and 4.2 V versus Li⁺/Li. AC impedance of the Li/Li₆V₁₀O₂₈ cell reveals that the cathode process is controlled mainly by Li⁺ diffusion in the active material. The novel material would be a promising cathode material for Li-ion batteries.     

Preparation and evaluation of α-Al2O3 supported lithium ion sieve membranes for Li+ extraction

Spinel lithium manganese oxide ion-sieves have been considered the most promising adsorbents to extract Li⁺ from brines and sea water. Here, we report a lithium ion-sieve which was successfully loaded onto tubular α-Al₂O₃ ceramic substrates by dipping crystallization and post-calcination method. The lithium manganese oxide Li₄Mn₅O₁₂ was first synthesized onto tubular α-Al₂O₃ ceramic substrates as the ion-sieve precursor (i.e. L-AA), and the corresponding lithium ion-sieve (i.e. H-AA) was obtained after acid pickling. The chemical and morphological properties of the ion-sieve were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Both L-AA and H-AA showed characteristic peaks of α-Al₂O₃ and cubic phase Li₄Mn₅O₁₂, and the peaks representing cubic phase could still exist after pickling. The lithium manganese oxide Li₄Mn₅O₁₂ could be uniformly loaded not only on the surface of α-Al₂O₃ substrates but also inside the pores. Moreover, we found that the equilibrium adsorption capacity of H-AA was 22.9 mg·g⁻¹. After 12 h adsorption, the adsorption balance was reached. After 5 cycles of adsorption, the adsorption capacity of H-AA was 60.88% of the initial adsorption capacity. The process of H-AA adsorption for Li⁺ correlated with pseudo-second order kinetic model and Langmuir model. Adsorption thermodynamic parameters regarding enthalpy (∆ H), Gibbs free energy (∆ G) and entropy (∆ S) were calculated. For the dynamic adsorption–desorption process of H-AA, the H-AA exhibited excellent adsorption performance to Li⁺ with the Li⁺ dynamic adsorption capacity of 9.74 mg·g⁻¹ and the Mn²⁺ dissolution loss rate of 0.99%. After 3 dynamic adsorption–desorption cycles, 80% of the initial dynamic adsorption capacity was still kept.     

Highly selective,regenerated ion-sieve microfiltration porous membrane for targeted separation of Li<Superscript>+</Superscript>

A novel adsorbent lithium ion-sieve membrane (LISM) toward Li⁺ was successfully prepared by the phase inversion technique using synthesized lithium ion-sieve ultrafine powder as the precursor, poly(vinylidene fluoride) (PVDF) as a binder, N,N-dimethylacetamide (DMAc) as the solvent. The key design for the synthesis of LISM is the formation of lithium ion-sieve dropping with PVDF powder to obtain a highly selective adsorbent. The prepared LISM have been characterized. The X-ray diffraction illustrated that the synthesized lithium ion-sieve were purity phase cubic spinel structure, the scanning electron microscopy shown that the LISM with a poriferous surface morphology and lithium ion-sieve equably dispersed on the surface of the membrane. The membrane flux (9.7 mL cm^?1 min^?1) suggested that the LISM achieved high hydrophily and stability. The maximum adsorption capacity is 27.8 mg g^?1 in a high adsorption rate towards Li⁺ within 60 min. In addition, the LISM has excellent adsorption selectivity, since the separation factor α is 4.76 with respect to Mg²⁺. Overall results revealed that the LISM as a good candidate for Li⁺ separation and concentration from salt lake brine with a relatively high value of Mg²⁺/Li⁺ ratio.     

Microwave assisted hydrothermal synthesis of MnO2·0.5H2O ion-sieve for lithium ion selective adsorption

Li_1.6Mn_1.6O₄ (LMO) synthesized by microwave assisted hydrothermal method were used to obtain MnO₂·0.5H₂O ion sieves (HMO) after acid treatment. The HMO-1 prepared with a Li/Mn molar ratio of 4, at 100ºC for 1 h under microwave irradiation, exhibits an effective Li⁺ adsorption capacity of 5.6 mmol·g^?1 and a high selectivity to Li⁺ with an equilibrium distribution coefficient of 12366.44 mL·g^?1. Moreover, it shows almost saturated ion-exchange capacity (> 95%) for Li⁺ extracted/inserted process. Thus HMO ion-sieves with high adsorption capacity and selectivity to Li⁺ are expected to be a promising application for Li⁺ selective adsorption from brine, seawater, and aqueous lithium generated in industries.     

Nanowires embedded porous TiO2@C nanocomposite anodes for enhanced stable lithium and sodium ion battery performance

A porous carbon nanocomposite with embedded TiO₂ nanowires (NWs) was synthesized using a two-step synthetic method in which carbon matrix was obtained by carbonizing a vacuum dried gel. This unique structure in which TiO₂ nanowires uniformly distributed in and tightly bonded to the carbon matrix shortened the electron transport path and reduced the transmission resistance. Nanoporous structure ensured continuous transfer of Li⁺/Na⁺ and supplied a large specific surface area of 280.82 m² g⁻¹ to provide more active sites. Different from other existing works on TiO₂@C anode materials with TiO₂ loading higher than 60 wt%, the obtained very small amount of TiO₂ (~12 wt%) improved the electrochemical and long-cycle performance of carbon substrate with TiO₂ NWs embedded significantly, due to uniformly distributed TiO₂ NWs throughout the carbon matrix. These TiO₂@C composite anodes could deliver a specific capacity of 286 mA h g⁻¹ at 0.3 C, 197 mA h g⁻¹ at 0.15 C for lithium and sodium ion batteries, respectively. It maintained remarkably stable reversible capacities of 128 and 125 mA h g⁻¹ for lithium and sodium ion batteries at 3 C during 2500 cycles, respectively. Smaller fluctuations and smoother curves demonstrated that sodium ion storage was more stable than lithium ion storage for the TiO₂@C composite anode. In addition, the capacitive contributions of TiO₂@C in both systems are quantified by kinetics analysis.     

Influence of helium ion radiation on the nano-grained Li2TiO3 ceramic for tritium breeding

Lithium titanium oxide (Li₂TiO₃) tritium breeder ceramic plates with nano- and coarse-grain size were fabricated. The preparation methods contained CTAB-modifying precursor, combining dry-pressing with isostatically cold-pressing, and calcinating at optimized sintering temperature in turn. Then their properties were characterized after radiation by 280 keV helium (He⁺) ion. Extensive characterization analyses were performed to reveal the changes in nano-grained and coarse-grained Li₂TiO₃ after radiation. They contained glancing angle X-ray diffraction (GIXRD), atomic force microscopy (AFM), electron spin resonance (ESR), and scanning electron microscopy (SEM). The results showed as follows, GIXRD peak position of the nano-grained Li₂TiO₃ was more stable than the coarse-grained Li₂TiO₃ after radiation. Nano-grained Li₂TiO₃ was less rough and swollen than the coarse-grained one after radiation. Nano-grained Li₂TiO₃ had more excellent structural stability and less defect concentration of Eʹ-center after radiation. As a result, nano-grained Li₂TiO₃ might have much better radiation tolerance than the coarse-grained one by comparing characterization results.     

球形离子筛吸附剂的制备及其锂吸附性能评价

利用琼脂糖溶液的溶胶凝胶性质,通过锐孔凝固浴法,对实验室合成的Li₄Mn₅O₁₂粉体进行成型,制备了粒径2～3 mm的球形颗粒,对球形颗粒进行交联后,用1 mol·L^-1的盐酸对球形颗粒进行酸洗脱锂,最终制得球形锂离子筛吸附剂。考察球形吸附剂制备和交联的影响因素,结果表明：5%的琼脂糖浓度和90 ℃的温度为最佳制备条件,2 ml·g^-1的交联剂用量和6 h的交联时间为最佳交联条件。对球形离子筛吸附剂进行静态评价实验,结果表明锂吸附容量为4.25 mmol·g^-1,吸附速率为1.77×10^-5 s^-1,成型后离子筛吸附量是离子筛粉末的75.6%,吸附速率较粉体（3.29×10^-4 s^-1）下降一个数量级。Li⁺平衡吸附容量随平衡pH值的升高而增加,在pH>12时吸附容量高达5.5 mmol·g^-1。共存离子选择性实验表明,交联球形离子筛吸附剂对Li⁺具有高选择性,成型后离子筛可以用于盐湖卤水或者海水提锂。     

Lithium sulfonate promoted compatibilization in single ion conducting solid polymer electrolytes based on lithium salt of sulfonated polysulfone and polyether epoxy

Polymeric lithium salts of sulfonated polysulfone (SPSU(X)Li) were synthesized via post sulfonation route followed by ion exchange. A novel single ion conducting solid polymer electrolyte (SPE) was prepared by curing poly(ethylene glycol)diglycidyl ether (PEGDGE) with 4,4′ diaminodiphenyl sulfone (DDS) in SPSU(X)Li matrix. The ionic conductivity, thermal stability and tensile properties were investigated as a function of degree of sulfonation and PEGDGE concentration. The introduction of lithium sulfonate groups in polysulfone promoted compatibility of SPSU(X)Li and PEGDGE in SPE. AFM analysis demonstrated heterogeneous phase morphology and reduction in size of dispersed PEGDGE phase with increasing degree of sulfonation. The interactions between lithium sulfonate and polyether epoxy improved thermal stability of the epoxy network. The enhanced compatibility also caused improvement in elongation at break compared to neat SPSU(X)Li. The higher Li⁺ ion concentration and the segmental mobility of the polymer chains above T_g contributed to the high ionic conductivity at high temperature in the single ion conducting SPE.     

Mechanical and electrochemical properties of cubic and tetragonal LixLa0.557TiO3 perovskite oxide electrolytes

Solid oxide electrolytes with high Li ion conductivity and mechanical stability are vital for all solid-state lithium ion batteries. The perovskite material Li_xLa_0.557TiO₃ with various initial Li (0.303 ≤ x ≤ 0.370) is synthesized by traditional solid-state reaction. The cubic and tetragonal structures are prepared with fast and slow cooling, respectively. The results reveal that the Li ion conductivity of the cubic structure is higher. In fact, the bulk conductivity of 1.65 × 10^?3 S cm^?1 is obtained at room temperature for x = 0.350. The crystal structure is not affected by the Li₂O quantity. In addition, Young's modulus, hardness, and fracture toughness are determined with indentation method for both structures. The Young's modulus increases with increasing Li₂O. However, hardness and fracture toughness keep a relatively stable value independent of Li₂O quantity.     

Synthesis of H2TiO3-PVC lithium-ion sieves via an antisolvent method and its adsorption performance

H₂TiO₃ is the most promising and highly selective lithium-ion sieve. In this study, HTO-PVC-x (x = 10, 15, 20, 25, and 30) lithium-ion sieves were prepared via an antisolvent method using PVC as the matrix. The X-ray diffraction (XRD) and scanning electron microscopy (SEM) results showed that Li₂TiO₃ was preferentially indexed to a C2/c monoclinic structure. LTO-PVC-x had a spherical size of 300 μm and an enormous specific surface area. The morphology and size of HTO-PVC-x obtained by HCl elution were consistent with those of LTO-PVC-x, indicating good separation and recycling properties. HTO-PVC-15 had a higher adsorption performance and adsorption capacity at a lower initial Li⁺ concentration. The adsorption behaviour of HTO-PVC-15 is in accordance with the Langmuir isothermal model and pseudo-second-order model, which belongs to the chemical adsorption process. It reached 96% of its equilibrium adsorption capacity within 2 h. Simultaneously, it maintained high adsorption selectivity and cycling performance and a low Ti⁴⁺ dissolution rate. Thus, HTO-PVC-15 has immense potential to be used for salt lake brine adsorption applications.     

Preparation and characterization of three dimensionally ordered macroporous Li4Ti5O12 anode for lithium batteries

Three dimensionally ordered macroporous (3DOM) Li₄Ti₅O₁₂ membrane (80 μm thick) was prepared by a colloidal crystal templating process. Colloidal crystal consisting of monodisperse polystyrene particles (1 μm diameter) was used as the template for the preparation of macroporous Li₄Ti₅O₁₂. A precursor sol consisting of titanium isopropoxide and lithium acetate was impregnated into the void space of template, and it was calcined at various temperatures. A macroporous membrane of Li₄Ti₅O₁₂ with inverse-opal structure was successfully prepared at 800 °C. The interconnected pores with uniform size (0.8 μm) were clearly observed on the entire part of membrane. The electrochemical properties of the three dimensionally ordered Li₄Ti₅O₁₂ were characterized with cyclic voltammetry and galvanostatic charge and discharge in an organic electrolyte containing a lithium salt. The 3DOM Li₄Ti₅O₁₂ exhibited a discharge capacity of 160 mA h g⁻¹ at the electrode potential of 1.55 V versus Li/Li⁺ due to the solid state redox of Ti^3+/4+ accompanying with Li⁺ ion insertion and extraction. The discharge capacity was close to the theoretical capacity (167 mA h g⁻¹), which suggested that the Li⁺ ion insertion and extraction took place at the entire part of 3DOM Li₄Ti₅O₁₂ membrane. The 3DOM Li₄Ti₅O₁₂ electrode showed good cycle stability.     

Electrochemical Recovery of Lithium Ions in the Aqueous Phase

Abstract

The electrochemical insertion of lithium ions into a Pt/λ-MnO₂ electrode was investigated in various metal chloride solutions. The Li⁺ insertion occurred effectively in LiCl solutions with higher concentration than 10 mmol/dm³, but it could hardly occur in a 0.1 mmol/dm³ LiCl solution. Alkaline earth metal ions showed a stronger inhibition effect against the Li⁺ insertion into the Pt/λ-MnO₂ electrode than alkali metal ions. However, since only Li⁺ ions were taken up from a mixed solution of lithium and alkaline earth metal chlorides, a high selectivity of the electrode for lithium ions was shown.

It was possible to recover lithium ions from geothermal water by this electrochemical method using the Pt/λ-MnO₂ electrode; the lithium uptake was 11 mg/g-MnO₂.     

Why is aluminum-based lithium adsorbent ineffective in Li+ extraction from sulfate-type brines

Aluminum-based lithium adsorbent (Li/Al-LDH) is the only industrialized adsorbent for Li⁺ extraction from salt lake brines. The inherent mechanism of declined Li⁺ adsorption performance was revealed to explain the feebleness in sulfate-type brines. SO₄²⁻ in brines could replace interlayer Cl⁻ by a stronger electrostatic attraction with laminates, significantly altering the stacking structure and interlayer spacing, while Cl K-edge of XAFS showed intercalated SO₄²⁻ would not obviously change the chemical environment of interlayer Cl⁻. Experiments as well as DFT and FEM simulations indicated the intercalated SO₄²⁻ regulated Li⁺ adsorption of Li/Al-LDHs at different ionic strength under a combined effect of expanded interlayers, close packing, and electrostatic repulsion. Although sufficient SO₄²⁻ contents in brines might promote the single Li⁺ adsorption by offering ionic strength as a driving force, the long-term usability would be severely impaired as SO₄²⁻ intercalation in interlayers reduced the subsequent Li⁺ adsorption capacity and increased the desorption difficulty.     

Lithium ion conductive behavior of TiO2 nanotube/ionic liquid matrices

A series of TiO₂ nanotube (TNT)/ionic liquid matrices were prepared, and their lithium ion conductive properties were studied. SEM images implied that ionic liquid was dispersed on the whole surface of TNT. Addition of TNT to ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMImTFSA)) resulted in significant increase of ionic conductivity. Furthermore, lithium transference number was also largely enhanced due to the interaction of anion with TNT. Vogel-Fulcher-Tammann parameter showed higher carrier ion number for TNT/BMImTFSA in comparison with BMImTFSA.     

Crystal structure of cubic Li7-3xGaxLa3Zr2O12 with space group of I-43d

Cubic Li_7-3xGa_xLa₃Zr₂O₁₂ is a cubic phase with a space group of I-43d instead of Ia-3d. This structure is more conducive to the migration of lithium ions. However, the effect of Ga on the size and environment of lithium ion transport channels has not been researched. In this work, Li_7-3xGa_xLa₃Zr₂O₁₂ (x = 0–0.25) was formulated, and the crystal structure was obtained by neutron diffraction. The results indicated that the minimum channel size to control Li⁺ migration in LLZO was the bottleneck size between the Li2 and Li3 sites (bottleneck size 2), and compared with lanthanum ions, the zirconium ions were closer to lithium ions. As the Ga content increased, bottleneck size 2 levelled off, while the lithium concentration and the distance between skeleton ions and lithium ions decreased. As a result, the lithium ionic conductivity primarily increased and then decreased. When doping 0.2 pfu of Ga, LLZO exhibited the highest lithium ionic conductivity of 1.45 mS/cm at 25 °C due to the coordinated regulation of Li⁺ concentration, bottleneck size, and the distance between skeleton ions and lithium ions.     

Potentiometric measurements and impedance characteristics of Li0.30La0.57TiO3 membrane in lithium anhydrous solutions

The potentiometric response of the Li⁺ ion-selective electrode based on the fast ion conductor Li_3xLa_2/3−xTiO₃ (x = 0.10) membrane (named LLTO) as well as the impedance of the LLTO membrane/Li⁺ solution in either anhydrous or hydrated PC solvent have been carried out. A four-electrode configuration has been used for the investigation of the interfacial phenomenon. It has been shown that the LLTO membrane can be used to detect the Li⁺ activity in anhydrous solutions through a Li⁺ ion exchange mechanism. The potentiometric response shows a Nernstian behavior with a Li⁺ sensitivity of −72 mV/decade at 25 °C. This high sensitivity can be correlated to a localised hydroxylation of the oxide surface with the residual water present in the solution in combination to the Li⁺ exchange reaction. An apparent standard current density of 12 μA/cm² and a charge-transfer coefficient of 0.29 have been determined. However, as water content in the electrolyte increases, the activity domain of the detection decreases to lead to the disappearance of the Li⁺ ion exchange mechanism in Li⁺ aqueous solution. This annihilation of the exchange process may be due to the predominant catalytic reaction of [Ti-O]⁻ with H₂O and/or to the formation of a water layer on the oxide surface.     

Synthesis of hollandite-type LixMnO2 by Li ion-exchange in molten salt and lithium insertion characteristics

The Li⁺ ion-exchange reaction of K⁺-type α-K_0.14MnO_1.93·nH₂O containing different amounts of water molecules (n = 0-0.15) with a large (2 × 2) tunnel structure has been investigated in a LiNO₃-LiCl molten salt at 300 °C. The Li⁺ ion-exchanged products were examined by chemical analysis, X-ray diffraction, and transmission electron microscopy measurements. The K⁺ ions and the hydrogens of the water molecules in the (2 × 2) tunnels of α-MnO₂ were exchanged by Li⁺ ions in the molten salt, resulting in the Li⁺-type α-MnO₂ containing different amounts of Li⁺ ions and lithium oxide (Li₂O) in the (2 × 2) tunnels with maintaining the original hollandite structure.The electrochemical properties and structural variation with initial discharge and charge-discharge cycling of the Li⁺ ion-exchanged α-MnO₂ samples have been investigated as insertion compounds in the search for new cathode materials for rechargeable lithium batteries. The Li⁺ ion-exchanged α-MnO₂ samples provided higher capacities and higher Li⁺ ion diffusivity than the parent K⁺-type materials on initial discharge and charge-discharge cyclings, probably due to the structural stabilization with the existence of Li₂O in the (2 × 2) tunnels.     

A novel lithium intercalation compound based on the layered structure of lithium nitridonickelates Li3−2xNixN

New lithium nickel nitrides Li_3−2xNi_xN (0.20 ≤ x ≤ 0.60) have been prepared and investigated as negative electrode in the 0.85/0.02 V potential window. These materials are prepared from a Ni/Li₃N mixture at 700 °C under a nitrogen flow. Their structural characteristics as well as their electrochemical behaviour are investigated as a function of the nickel content. For the first time are reported here the electrochemical properties of a lithium intercalation compound based on a layered nitride structure. The Li_3−2xNi_xN compounds can be reversibly reduced and oxidized around 0.5 V versus Li/Li⁺ leading to specific capacities in the range 120-160 mAh/g depending on the nickel content and the C rate. Due to a large number of lithium vacancies, the structural stability provides an excellent capacity retention of the specific capacity upon cycling.