Pure Lithium Research Articles

Effect of ZnO on sintering and microwave dielectric properties of 0.5CaTiO3-0.5 (Li0.5La0.5) TiO3 ceramics

The novel calcium titanate-lithium lanthanum titanate doped with zinc oxide (0.10, 0.30, and 0.50 mol. %) ceramic samples were prepared by solid-state reaction route. The phase formation, microstructure, densification, and microwave dielectric properties were investigated. It was found that the doping with zinc oxide led to a decrease in sintering temperature by 25 oC as compared with pure calcium titanate lithium lanthanum titanate due to the liquid phase effect. Also, the calcium titanate lithium lanthanum titanate (10ZCTLLT&30ZCTLLT)) doped with lower zinc oxide (0.10 and 0.30 mol. %) led to higher densification parameter. This was followed by increasing the zinc oxide doping up to (0.50 mol. %) which resulted in a decrease in densification and microwave dielectric properties which may be attributed to increase in porosity and grain growth upon the evaporation of zinc and oxygen vacancy. This led to the increase in dielectric loss (≈10 × 10−4) value with 50ZCTLLT. Hence, the best result of microwave dielectric characteristics was obtained for 0.5CaTiO3–0.5(Li0.5La0.5)TiO3 with (0.10 and 0.30 mol. % ZnO) 10ZCTLLT and 30ZCTLLT ceramic samples sintered at 1175 oC/2h, with low dielectric constant (εr) = 4.4–10.5, very low dielectric loss = 1.07-2.23 × 10−4 and high quality factor (Q x ƒ) ≈59-55 × 104 at 8 GHz. Consequently, they can be used not only in wireless satellite communications technology but also can be used in the fifth-generation telecommunication 5G technology construction.

Catalyst-free synthesis of lithium hydride at room temperature.

An organic solvent-assisted catalyst-free mechanochemical reaction is developed to synthesize lithium hydride at mild gas pressures and room temperature. Studies show that the formation of intermediates on the surface of bulk lithium metal is crucial for the synthesis of high purity (>98%) LiH. This provides a new strategy for the large-scale production of lithium-based hydrogen storage materials.

Features of the Defect Structure and Luminescence of Nominally Pure Lithium Niobate Crystals Produced Using Different Technologies.

We have established that luminescence in lithium niobate crystals both congruent and near-stoichiometric (R ≈ 1) is due to point defects in the cationic sublattice and intraconfigurational transitions in the oxygen-octahedral NbO6 clusters. We have also determined that the main contribution to the luminescence in the visible and near IR regions is made by luminescence centers with the participation of NbLi defects: the NbLi-NbNb bipolaron pair and the NbLi-O defect in a congruent crystal. The minimum intensity of bipolaron luminescence has been observed in stoichiometric crystals obtained using different technologies. Weak luminescence of the NbLi-NbNb bipolaron pair indicates a small number of NbLi defects in the crystal structure. The number of NbLi defects in the crystal structure indicates a deviation of the crystal composition from stoichiometry.

Нелинейно-оптические свойства кристаллов ниобата лития, легированных цинком

The coefficients of the second order nonlinear optical dij tensor were calculated by the method developed on the basis of the dielectrics theory of Phillipson and Van Wetchen and the Levin charge coupling model for lithium niobate crystals doped with zinc (3.43–5.84 mol %). In LiNbO3 : Zn crystals, the concentration dependences of the nonlinear optical coefficients showed several regions with maxima and minima; the most noticeable changes in the nonlinear optical coefficients were observed at threshold concentrations of zinc oxide in the melt. Doping with zinc increases the conversion efficiency of the second harmonic radiation, such the crystals are more promising for use in nonlinear optics than a nominally pure lithium niobate crystal.

Preparation of LiFePO4 composite based on dual carbon sources of phytic acid and glucose and its performance for lithium extraction from salt lake

In this study, biomass phytic acid (PhyA) was used as phosphorus source and internal carbon source, and glucose (GC) was used as external carbon source to prepare dual carbon source LiFePO4 (GC/IC/LFP) electrode material containing intercalated carbon (IC) and coated carbon (GC). Based on the working principle of rocking chair lithium ion battery, a new electrochemical system was constructed to efficiently extract Li+ from salt lake brine with high Mg/Li ratio (53) and Na/Li ratio (416). The effects of electrolytic voltage and coexisting ions on the capacity of lithium extraction/insertion at room temperature were investigated. It was found that when the electrolytic voltage was 1.0 V, the insertion capacity of lithium in pure lithium solution could reach 43.67 mg·LiFePO4 (1 g)−1, which was 99.25 % of the theoretical capacity (44 mg). The lithium extraction capacity can reach 43.20 mg·LiFePO4 (1 g)−1, which is 98.92 % of the insertion capacity. In the simulated salt lake brine with a large number of coexisting ions, when the electrolytic voltage is 0.8 V, the lithium insertion capacity can reach 38.09 mg·LiFePO4 (1 g)−1, which is 86.57 % of the theoretical capacity, and the lithium extraction capacity can reach 35.00 mg·LiFePO4 (1 g)−1, which is 91.89 % of the insertion capacity. The system maintains high selectivity for Li+ extraction. The concentration of coexisting ions of K+, Mg2+, Na+ and Ca2+ decreased by more than 8800, 4500, 25,000 and 1200 times, respectively. The Mg/Li ratio decreased from 53 to 0.09, and the Na/Li ratio decreased from 416 to 0.10. After ten times of extraction, the electrode still has high coexisting Men+/Li+ separation performance, although the extraction performance is decreased to a certain extent.

TG, DSC, XRD, and SEM studies of the substituted lithium ferrite formation from milled Sm2O3/Fe2O3/Li2CO3 precursors

Formation of substituted lithium ferrite Li0.5SmxFe2.5–xO4 (where x = 0.06 and 0.2) from Sm2O3/Fe2O3/Li2CO2 precursors was studied by X-ray diffraction analysis, thermogravimetry, differential scanning calorimetry, and scanning electron microscopy. The mixture of powders was subjected to preliminary mechanical activation in a planetary mill. We analyzed samples based on the precursors and synthesized at 900 °C for 4 h in a laboratory furnace. It was found that ball milling of the precursors mixture in a planetary mill increases the powder reactivity. In spite of this, no substituted lithium ferrites were formed. It was shown that a two-phase composite that consists of pure lithium ferrite Li0.5Fe2.5O4 and SmFeO3 is formed during synthesis. An increase in the Sm2O3 content in the initial mixture provides an increase in the amount of the formed SmFeO3 phase. The synthesis of Li0.5Fe2.5O4 ferrite was confirmed by XRD analysis data, the Curie temperature (627–630 °C) measured using TG analysis in a magnetic field, and by the presence of an endothermic peak on the DSC curve corresponding to the order–disorder transition in the Li0.5Fe2.5O4 phase.

(Digital Presentation) Engineering Electrode Architecture and Interfacial Chemistry of High-Content, High-Loading Silicon Anodes to Improve Cycle and Calendar Life

Silicon lithium alloys (SiLix) as the anode active material in a Li-Ion battery configuration offers possible energy densities paralleled only by pure lithium metal. However, the extreme mechanical deformation of alloying and dealloying SiLix through charge/discharge cycles paired with the highly reactive interface of SiLix are large barriers to industrial adoption of high-silicon-content negative electrodes. Moreover, these challenges are magnified when the thickness of the electrode is brought to relevant levels (>3 mg/cm2). Here, I describe efforts to address these challenges by utilizing single-nanometer-scale silicon nanoparticles to reduce capacity fade related to mechanical failure. I also detail new interfacial chemistries which give rise to precise electrode-level engineering in which the SEI morphology and thickness can be controlled. This development has enabled a 75% by mass silicon composite electrode to achieve cycle capacity retention of 73% through 1000 charge/discharge cycles against capacity-matched NMC-based cathodes. Figure 1

Thermal Stability of Active Materials Versus Different Type of Electrolytes

The safety of Lithium ion battery (LIB) is recently a hot topic due to their increased use by the electric vehicles. Energy density has become more and more important to solve the range anxiety. However, thermal behavior becomes more unstable due to this increase in energy density. Several studies have claimed that the main reason batteries have thermal runaway events are the reactions between the intercalated lithium in the anode and the liquid electrolytes [1] [2]. Therefore, solid state electrolytes are proposed [3] [4] to be an option to increase the thermal stability of LIBs.In this work, thermal evaluation of Solid state battery materials will first be defined by a differential scanning calorimeter to understand the thermal stability of the different materials that might be used in different types of solid state cells. Materials tested include layered oxide cathodes with different Ni content, pure lithium metal and several types of solid electrolytes such as sulfides, polymers and oxides. Heat flow test with different combinations of the materials, such as cathode with anode, cathode with electrolytes and anode with electrolytes were conducted to isolate reaction mechanisms between the different materials. The results show, that compared to the thermal runaway paths of cell with liquid electrolytes, sulfide and oxide electrolytes show the possibility of improved thermal stability. However, polymer electrolytes might have the similar, or even worse, thermal behavior as liquid electrolytes.Reference[1] Ren, X. Feng, L. Liu, H. Hsu, L. Lu, L. Wang, X. He and M. Ouyang. "Investigating the relationship between internal short circuit and thermal runaway of lithium-ion batteries under thermal abuse condition." Energy Storage Materials, 2021.[2]Mukai, T. Inoue and K. "Are All-Solid-State Lithium-Ion Batteries Really Safe?−Verification by Differential Scanning Calorimetry with an All-Inclusive Microcell." ACS Applied Materials & Interfaces, 2016.[3]Chen, A. M. Nolan, J. Lu, J. Wang, X. Yu, Y. Mo, L. Chen, X. Huang and H. Li. "The Thermal Stability of Lithium Solid Electrolytes with Metallic Lithium." Joule, 2020.[4]Feng, M. Ouyang, X. Liu, L. Lu, Y. Xia and X. He. "Thermal runaway mechanism of lithium ion battery for electric vehicles: A review." Energy Storage Materials, 2018. Figure 1

Is it possible to recover lithium compounds from complex brines employing electromembrane processes exclusively?

Research to develop direct lithium extraction technologies from aqueous sources is fundamental due to the environmental and techno-economic shortcomings of the evaporitic technology currently in use. Electromembrane processes are an attractive alternative since they could be much faster, more readily adaptable to brines of different compositions, sustainable since they use electrons as reactants, avoiding waste production, the use of chemicals, and decreasing the water footprint. Valuable Li + ions are only a very minor component in a complex matrix of very high ionic strength with co-existing cations, most importantly Mg 2+ and Na + , displaying similar chemical properties. A review from the recent literature shows that adaptation from the simple electrodialysis configuration will be needed to selectively recover pure lithium products. Testing of the proposed methodologies at meaningful concentrations, representative of real brines is key to bring these closer to industrial scale applications. • Li + cations are a minor component in a complex matrix of high ionic strength. • Reported selective separation higher than 99% of Li + from divalent cations. • Very few results where selective separation of Li + from Na + and K + are reported. • For Li + insertion electrodes high selectivity reported for lithium capture. • Electromembrane processes coupled to selective crystallization produce pure Li 2 CO 3 .

Biodiesel Production Using Lithium Metasilicate Synthesized from Non-Conventional Sources.

A facile and versatile process to produce lithium metasilicate (Li2SiO3) from non-conventional silicon sources (two different sand sources from the central area of México) was developed. The synthesis protocol based on a solid-state reaction followed by a hydrothermal treatment resulted in highly pure lithium metasilicate, as corroborated by XRD, SEM-EDS, and XPS analysis. Furthermore, lithium metasilicate was used as a heterogeneous catalyst for biodiesel production from soybean oil, where conversion yields were compared according to the silicon source used (based on chemical purity, stability, and yield efficiency). The best performing metasilicate material displayed a maximum of 95.5% of biodiesel conversion under the following conditions: 180 min, 60 °C, 5% catalyst (wt./wt., catalyst-to-oil), and 18:1 (methanol:oil). This contribution opens up alternatives for the production of lithium metasilicate using non-conventional precursors and its use as an alternative catalyst in biodiesel production, displaying better chemical stability against humidity than conventional heterogeneous catalysts.

Directional High-Value Regeneration of Lithium, Iron, and Phosphorus from Spent Lithium Iron Phosphate Batteries

As lithium-ion batteries (LIBs) are undergoing unprecedented development in electric vehicles (EVs) and renewable grids, recycling spent battery disposal is becoming the dominating issue considering the urgent demand for sustainable resources and eco-friendly development. However, existing recovery methods for spent LIBs still suffer from complex processes and low processing efficiency. Herein, an effective pyroprocessing-based strategy was proposed to recycle spent lithium iron phosphate (LFP) materials, featuring full element regeneration and conversion of high-value products. Specifically, over 99% Li was extracted and converted into high purity lithium carbonate (>99%), while Fe and P were further converted into value-added Fe2P2O7 and Na4P2O7, respectively. Due to the benefits of high efficiency of metal extraction and the reuse of all valuable elements, the pyroprocessing-based strategy potentially generates the profit of 1.44 $ kg–1 of LFP batteries, over three times more than that of the conventional hydrometallurgical process, while the discharges of wastewater and residue are reduced by 66.3 and 93.9%, respectively. This study provides a new pyroprocessing-based approach to the green recovery of all elements of LFP materials in spent LFP batteries.

Conductive domain walls in x-cut lithium niobate crystals

Conductive ferroelectric domain walls have been the focus of intensive studies in nanoelectronics due to their promising electronic properties. Here, both head-to-head and tail-to-tail domain walls with a large inclination angle (≈90°) were fabricated on the surface of x-cut nominally pure congruent lithium niobate crystals. Our results show that both types of domain walls are conductive, while the conductivity of the head-to-head domain walls is larger than that of the tail-to-tail domain walls by about two orders of magnitude at the same inclination angle of domain walls.

High Voltage LiCoO2 Cathodes with High Purity Lithium Bis(oxalate) Borate (LiBOB) for Lithium-Ion Batteries

High Voltage LiCoO₂ Cathodes with High Purity Lithium Bis(oxalate) Borate (LiBOB) for Lithium-Ion Batteries

Enhancing the electrochemical stability of lithium anode by introducing lithiophilic three-dimensional framework Li2Cu3Zn

As we all known, the most promising alternative anode for the next-generation energy storage devices is the lithium metal anode. But the unpredictable dendrite growth and volume expansion during the cycles impedes its applications and commercialization. The Li-Cu-Zn three-phases alloy materials (including Li2Cu3Zn, Li-Zn and Li) have been synthesized to solve these problems. According to the density functional theory (DFT) analysis, all results indicate that the Li2Cu3Zn ternary alloy has the higher absorption energy of Li than bare Li, suggesting the superior lithiophilic. Meanwhile, the construction of Li2Cu3Zn alloy 3D skeleton is beneficial to uniform the Li+ flux and reducing the local current density. Furthermore, based on the analysis of in-situ X-ray diffraction, Li2Cu3Zn skeleton can keep stable during the cycles. The Li-Cu-Zn electrodes exhibit the stable cycling performance about more than 1200 h and pure lithium only for about 120 h (at 1 mA cm−2 and 1 mAh cm−2). And at 0.5 C, after 100 cycles, the NCM811 (LiNi0.8Co0.1Mn0.1O2) ||Li-Cu-Zn cell delivers an excellent cycling stability for 92.3% capacity retention. In this work, uniform deintercalation of lithium ions through three-dimensional alloy framework structure provides a research basis for lithium-free anodes.

(Digital Presentation) Understanding the Impact of Process Conditions on Manufacturing Thick Cathodes By Systematically Reducing Inactive Material Percentages

With the lithium-ion battery industry moving to high energy density anode materials such as silicon and lithium metal as a substitute for lower specific capacity carbon-based materials like graphite, cathode energy density can become a bottleneck. Typical cathodes have less than 10% practical specific capacity compared to both pure lithium metal and silicon. For these anodes, cathodes with higher active material loadings per unit area would be needed to produce matching electrode pairs. However, cathode thickness cannot indefinitely be increased, as doing so leads to issues with electrolyte transportation, conductivity, and mechanical properties [1,2].Increasing the loading of the cathode could also be done by reducing the amounts of inactive components, such as the binder and the conductive additive, in the electrode. To achieve this, understanding the role of each component is important. The most important role of the binder is to act as an adhesive among particles and the current collector. But most binders are electronically insulating. The main role of the conductive additive, such as carbon black, is to improve the conductivity of the overall system [1].As the inactive material percentages are decreased, the distribution of these components in the electrode domain becomes more important to both the electrochemical and mechanical performance of the electrode. The distribution changes with the different process conditions used, such as mixing techniques, order, speeds, times, slurry viscosity, drying conditions, etc. This research consists of a systematic study to understand the effects of the aforementioned process conditions on the particle and polymer distribution as well as its contribution to the mechanical and electrochemical performance. With the use of the current findings, the active material percentage was increased up to 98% in electrodes with 5 mAh/cm2 loading, retaining similar performance to electrodes with 92.8% active material, as shown in figure 1. Some contribution of the capacity fade was found to be due to the lithium counter electrode used.The goal of this ongoing project is to produce a model that could be applied to different materials to identify the best process conditions for thick electrode manufacturing.References F. Ma, Y. Fu, V. Battaglia, R. Prasher, Microrheological modeling of lithium-ion battery anode slurry, J. Power Sources, 438 (2019), p. 226994Wen Yu, Nanping Deng, Lin Tang, Kewei Cheng, Bowen Cheng, Weimin Kang, Roles of metal element substitutions from the bimetallic solid-state electrolytes in lithium batteries, Particuology, 65 (2022), p. 51-71 Figure 1

Effect of carbon reinforcement on the EMI shielding response of LiFe5O8 ceramics

Carbon black (CB) reinforced lithium ferrite composites (LFO/CB) are synthesized to enhance EMI (electromagnetic interference) shielding effectiveness (SE) as nowadays EMI pollution is becoming a serious matter of concern for technology as well as human health. The formation of pure phase lithium ferrite and composites are analyzed. Though saturation magnetization decreased with the incorporation of CB, it did not create any huge decrement. Shielding efficiency is analyzed in the X band (8.2–12.4 GHz) and Ku (12.4–18 GHz) band frequency range. The highest total SE (28 dB) is obtained for 20 wt% of CB with LFO (3 mm thickness), out of which reflection-based shielding effectiveness (SER) is 4.58 dB and absorption based (SEA) is 23.17 dB. The highest absorption efficiency of the composites is measured to be ~99.68% for both LFO/CB (15) and LFO/CB (20) in the broad frequency range (8.2–18 GHz), which confirmed that the composite provides absorption-based SE rather than reflection based. Both real and imaginary part of permittivity drastically increased with incorporation of CB concentration (LFO: ε’ = 4, ε“= 0.11; LFO/CB (20) : ε’ = 46, ε”= 19.05 @8.2 GHz). Complex permeability also increased with CB content. However, dielectric, magnetic, and EMI shielding responses can be tailored by governing the amount of ferrite as well as carbon compound. Further, this study confirms that LFO/CB composites can be a potential candidate for application in the defense and telecommunication sector.

High-Pressure Synthesis and Stability Enhancement of Lithium Pentazolate.

The pentazolate anion, cyclo-N5-, has received extensive attention as a new generation of energetic species for explosive or propulsion applications. Binary pentazolate compounds have been obtained under high-pressure conditions and their stability enhancement is crucial for obtaining more competitive high energy density materials (HEDMs). Here, we report the synthesis of a new solid phase of lithium pentazolate (space group P21/c) through the chemical transformation of pure lithium azide under high-pressure and high-temperature conditions. Upon decompression, the structural transition from P21/c-LiN5 to P21/m-LiN5 at ∼15.6 GPa was observed for the first time. Cyclo-N5- can be traced down to ∼5.7 GPa at room temperature and recovered to ambient pressure under a low-temperature condition (80 K). Our results reveal the enhancement of pentazolate anion stability with the increasing content of metal cations and demonstrate that low temperature is an effective route for the recovery of the pentazolate anion.

Synthesis, characterization, and DFT Raman study of pure and Mn‐doped LiTaO3 nanofibers

AbstractPure and Mn‐doped lithium tantalate nanofibers, with Mn concentrations of 1%, 2.5%, and 5%, were synthesized by the electrospinning method. The morphology, microstructure, and crystal structure of as‐spun and annealed composite nanofibers were characterized by scanning electron microscopy, X‐ray diffraction, and transmission electron microscopy. Raman spectroscopy has shown to be a powerful tool to detect either local variations or changes of the whole structure. Position and width of one Raman line can be used as markers of a structural change. Some vibrational modes are especially associated with the site of Li or Ta ions and so, they can be affected by the introduction of dopant ions. Any damages or local changes in the microstructure can be detected by a line broadening. With the use of Raman spectroscopy, the sites where Mn ions enter the doped structures were established by recording the shift and broadening of peaks in Mn‐doped structures with respect to pure lithium tantalate. Thus it was proven that Mn ions enter the Li sites for low Mn concentration and, on the other hand, for higher concentrations, the dopant substitutes Li and Ta sites. First‐principles calculations were performed within the density functional theory, including lattice‐dynamic calculations of the phonon modes at the zone center (Γ point), for the pure structure, to find the irreducible representation of the modes.

Rational surface engineering of Ti3C2Tx MXene for high-performance lithium-sulfur batteries

Ti3C2Tx MXene has attracted great attention in lithium-sulfur batteries (LSBs) because of its multi-layer structure. However, the low adsorption strength between pure Ti3C2Tx and lithium polysulfides (LiPSs) causes inferior capacity. Surface modification is a promising methode to improve LiPSs adsorption strength of Ti3C2Tx.Herein, we report afast method for rationalsurface engineering of Ti3C2Tx in this paper. One-step plasma treatment strategy is applied to prepare nitrogen-doped Ti3C2Tx (Ti3C2Tx-N) in the first time. SEM and EDS mapping images show that the homogenous nitrogen doped on Ti3C2Tx. Due to the strong interaction between nitrogen in Ti3C2Tx with LiPSs along with high electronical conductivity, the S/MXene-N composite demonstrates excellent electrochemical performances, including high initial reversible capacity (1281.2 mAh g−1 at 0.5 C) and high cycling stability (420.3 mAh g−1 at 2.0 C after 1000 cycles). Overall this work offers a simple surface engineering strategy to manipulate Ti3C2Tx towards high-performance LSBs’ cathodes host.

Development of a methodology for the analysis of a fuel composition based on lithium and beryllium fluorides by atomic emission arc spectrometry

An atomic emission technique for the analysis of a fuel salt containing uranium and a coolant based on lithium and beryllium fluorides has been developed and tested. When developing the technique, the conditions accepted at Rosatom enterprises for the analysis of beryllium oxide and lithium carbonate were taken into account. The complexity of the structure of the arc spectrum of the matrix is noted. X-ray phase analysis of the sample residues in the electrodes revealed that the source of molecular bands in the spectra is lithium fluoroberillate. The analytical lines of Al, B, Ca, Cd, Cr, Cu, Fe, Mg, Ni, Pb, Si and Zn, free from overlap with the lines of the molecular spectrum and uranium were selected. A method of extreme experiment design is used to select optimal conditions for the arc excitation of the sample: the type and strength of the discharge current (alternating current 12 A), exposure time (20 sec), the shape of the electrode («glass») and the mass of the material (30 mg). Recommendations are given and implemented for the preparing samples for calibration using pure lithium fluoroberillate as a matrix material when introducing controlled elements in the form of certified reference materials of graphite (graphite collector of trace impurities). Calibration graphs in logarithmic coordinates are linear with angular coefficients close to unity. The metrological characteristics of the technique are evaluated in analysis of real samples: the repeatability, intermediate precision of the results and the limits of the element detection.