High Lithium Content Research Articles

Fast Charge/Discharge of Li Metal Batteries Using an Ionic Liquid Electrolyte

Because of their potentially superior safety characteristics, room temperature ionic liquids (RTILs or ILs) have been vigorously researched as a potential replacement for current commercial lithium battery electrolytes, which are based on volatile and flammable organic carbonates. However, relatively poor battery performance, which is a consequence of the higher viscosity and lower conductivity of these materials, has prevented them becoming mainstream electrolytes for commercial lithium batteries. Amongst various RTILs, those containing the bis(fluorosulfonyl)imide (FSI) anion exhibit high conductivities and diffusivities, making them interesting potential electrolytes for lithium metal batteries. Here, we evaluate the electrochemical stability, lithium electrochemistry, and Li+ transference numbers of FSI-based ionic liquid electrolytes intended for use in rechargeable Li metal batteries. We show that ILs containing high concentrations of lithium, up to 3.2 mol.kg−1 in C3mpyr FSI, have excellent rate capability (higher than that of standard battery electrolytes) with both the lithium metal electrode and LiCoO2 cathode, in spite of their significantly higher viscosities and lower conductivities. This unusual behavior is ascribed to the concomitant increase in transference number with increasing Li-salt concentration.

Kurnakovite deposits on the Qinghai-Tibet Plateau (II): an investigation from chemical kinetics of chloropinnoite dissolution

Lakes on the Qinghai-Tibet Plateau (QTP) are of particular interest to researchers because of their unusual high concentrations of lithium (Li), boron (B), and potassium (K). Kurnakovite, a member of the inderite group, is well-distributed on the QTP, however, the geochemical mechanisms of kurnakovite transformation requires further identification and clarification. This study aims to elucidate the geochemical mechanisms of kurnakovite deposits on the QTP from chloropinnoite dissolution using chemical kinetic and spectroscopic techniques. The new borate, chloropinnoite 2MgO · 2B2O3 · MgCl2 · 14H2O, was obtained from the natural concentrated salt lake brine on the QTP. The kinetics of chloropinnoite dissolved in 4.5 % (wt%) boric acid solution at 303, 313, and 323 K were investigated. The characterization of the phase transitions and the kinetics were carried out by chemical titration analysis, X-ray powder diffraction spectrometry, Fourier Transform Infrared (FT-IR), and Raman spectrometry. The results demonstrate that similar kinetic processes occur at all three temperatures and can be divided into dissolution, supersaturation, and precipitation, according to three distinct kinetic curves. Kurnakovite was the final phase transition (terminal secondary mineral) within the chloropinnoite-boric acid solution. The dissolution rate of chloropinnoite (the dissolution stage) could be described by second order pseudo-homogeneous reaction model. According to the spectroscopy data, geochemical mechanism of kurnakovite was identified. The new geochemical hypothesis well explains the geochemical mechanism of kurnakovite minerals on the QTP.

Ferromagnetism in Li doped ZnO nanoparticles: The role of interstitial Li

ZnO nanoparticles doped with Li (Zn1−yLiyO, y ≤ 0.1) have been investigated with emphasis on the correlation between their magnetic, electronic, and structural properties. In particular, defects such as interstitial Li and Zn atoms, substitutional Li atoms, and oxygen vacancies have been identified by X-ray photoelectron spectroscopy (XPS) and their respective roles in stabilization of the magnetic moment are discussed. X-ray diffraction (XRD) and XPS give clear evidence of Li presence at both substitutional and interstitial sites. XPS studies further show that the amount of substitutional Li defects (Lizn) and interstitial Li defects (Lii) vary non-monotonically with the Li concentration, with the Lii defects being noticeably high for the y = 0.02, 0.08, and 0.10 concentrations, in agreement with the XRD results. Magnetization studies show room temperature ferromagnetism in these nanoparticles with the moment being largest for the particles with high concentration of interstitial lithium and vice versa. Both interstitial Zn (Zni) defects and Zn-O bonds were determined from the Zn LMM Auger peaks; however, the variation of these with Li concentrations was not large. Oxygen vacancies (Vo) concentrations are estimated to be relatively constant over the entire Li concentration range. We relate the Lii and Zni defects to the formation and stabilization of Zn vacancies and thus stabilizing the p-type ferromagnetism predicted for cation (zinc) vacancy in the ZnO type oxides.

Copper Silicides with the Highest Lithium Content: Li7CuSi2 Containing the 16‐Electron Group [CuSi2]7− and Li7.3CuSi3 with Heterographene Nets ${{{\hfill 2\atop \hfill \infty }}}$[CuSi]3.3−

Incredibly rich in lithium: The ternary silicides Li7CuSi2 with the linear [Si-Cu-Si]7− Zintl anion (see picture) and Li7.3CuSi3 are compounds with the highest lithium content in the ternary system. The crystal and electronic structures of both compounds are discussed.

Copper Silicides with the Highest Lithium Content: Li7CuSi2 Containing the 16‐Electron Group [CuSi2]7− and Li7.3CuSi3 with Heterographene Nets ${{{\hfill 2\atop \hfill \infty }}}$[CuSi]3.3−

Jede Menge Lithium: Die Silicide Li7CuSi2, mit dem linearen Zintl-Anion [Si-Cu-Si]7− (siehe Bild), und Li7.3CuSi3 sind die Verbindungen mit dem höchsten Lithiumgehalt in diesem ternären System. Die Kristallstrukturen und Bindungsverhältnisse beider Verbindungen werden besprochen.

Discovery and preliminary study of the high tungsten and lithium contents in the Dazhuyuan bauxite deposit, Guizhou, China

Bauxite in China remains an urgently needed resource largely dependent on imports. Based on the study of the newly-discovered Dazhuyuan bauxite deposit in northeastern Guizhou, we have found new enrichment of tungsten and lithium in bauxite, with the highest WO3 content up to 0.33% and the highest Li2O content up to 0.58%. The present paper reports the initial result, and the spatial distribution feature of W and Li in the ore body (with Li enriched mostly in the north part of the west limb of the Liyuan syncline, whereas W enriched mostly in the central part of the east limb). The results suggest that it is necessary to delineate lithium and tungsten ore body independently, discuss the feasibility of its industrial utilization, and point out the new direction of synthetic appraisal for such kinds of traditional mineral resources, in order to forecast and assess bauxite resources in the region.

Crossing the Gould Belt in the Orion vicinity

We present a study of the large-scale spatial distribution of 6482 RASS X-ray sources in approximately 5000 deg^2 in the direction of Orion. We examine the astrophysical properties of a sub-sample of ~100 optical counterparts, using optical spectroscopy. This sub-sample is used to investigate the space density of the RASS young star candidates by comparing X-ray number counts with Galactic model predictions. We characterize the observed sub-sample in terms of spectral type, lithium content, radial and rotational velocities, as well as iron abundance. A population synthesis model is then applied to analyze the stellar content of the RASS in the studied area. We find that stars associated with the Orion star-forming region do show a high lithium content. A population of late-type stars with lithium equivalent widths larger than Pleiades stars of the same spectral type (hence younger than ~70-100 Myr) is found widely spread over the studied area. Two new young stellar aggregates, namely "X-ray Clump 0534+22" (age~2-10 Myr) and "X-ray Clump 0430-08" (age~2-20 Myr), are also identified. The spectroscopic follow-up and comparison with Galactic model predictions reveal that the X-ray selected stellar population in the direction of Orion is characterized by three distinct components, namely the clustered, the young dispersed, and the widespread field populations. The clustered population is mainly associated with regions of recent or ongoing star formation and correlates spatially with molecular clouds. The dispersed young population follows a broad lane apparently coinciding spatially with the Gould Belt, while the widespread population consists primarily of active field stars older than 100 Myr. We expect the "bi-dimensional" picture emerging from this study to grow in depth as soon as the distance and the kinematics of the studied sources will become available from the future Gaia mission.

Characterization of lithium borophosphate glass thin film electrolytes deposited by RF-magnetron sputtering for micro-batteries

Lithium ion conducting thin film electrolytes, Li2O-B2O3-P2O5 glass systems, were prepared with a wide range of chemical composition by co-sputtering method with multi-targets. The maximum ionic conductivity at room temperature was 1.22×10−6S/cm and the activation energy of this specimen was 0.54eV when enhanced by the mixed former effect and the high network modifier content. The increased ion conductivity of the films appeared to be associated with the formation of stable tetrahedral borate at high lithium concentration and this structural change facilitated faster ion migrations. The relationship between the glass structure and electrical performance of the mixed former glasses was investigated by the infrared spectra analysis of borate networks. The conductivity of the mixed former electrolytes increased gradually with increasing the RF power on Li2O target, and the maximum conductivity was obtained at 100W. The structural role of the network modifier in xLi2O-(1-x)(B2O3-P2O5) glasses was analyzed by the O1s spectra of X-ray Photoelectron Spectroscopy. A quantitative deconvolution of O1s spectra suggests that the increased conductivity with increasing lithium content is due to the formation of non-bridging oxygen.

Neuroprotective effects of chronic exposure of SH-SY5Y to low lithium concentration involve glycolysis stimulation, extracellular pyruvate accumulation and resistance to oxidative stress

Recent studies suggest that lithium protects neurons from death induced by a wide array of neurotoxic insults, stimulates neurogenesis and could be used to prevent age-related neurodegenerative diseases. In this study, SH-SY5Y human neuronal cells were cultured in the absence (Con) or in the presence (Li+) of a low lithium concentration (0.5 mm Li2CO3, i.e. 1 mm lithium ion) for 25-50 wk. In the course of treatment, growth rate of Con and Li+ cells was regularly analysed using Alamar Blue dye. Resistance to oxidative stress was investigated by evaluating: (1) the adverse effects of high concentrations of lithium (4-8 mm) or glutamate (20-90 mm) on cell growth rate; (2) the levels of lipid peroxidation (TBARS) and total glutathione; (3) the expression levels of the anti-apoptotic Bcl-2 protein. In addition, glucose metabolism was investigated by analysing selected metabolites in culture media and cell extracts by 1H-NMR spectroscopy. As compared to Con, Li+ cells multiplied faster and were more resistant to stress, as evidenced by a lower dose-dependent decrease of Alamar Blue reduction and dose-dependent increase of TBARS levels induced by toxic doses of lithium and glutamate. Total glutathione content and Bcl-2 level were increased in Li+ cells. Glucose consumption and glycolytic activity were enhanced in Li+ cells and an important release of pyruvate was observed. We conclude that chronic exposure to lithium induces adaptive changes in metabolism of SH-SY5Y cells involving a higher cell growth rate and a better resistance to oxidative stress.

Geothermal constraints on enrichment of boron and lithium in salt lakes: An example from a river-salt lake system on the northern slope of the eastern Kunlun Mountains, China

Some rivers on the northern slope of the eastern Kunlun Mountains in the Qaidam Basin, China, show very high concentrations of boron and lithium. Correspondingly, the salt lakes fed by these rivers show an unusual enrichment of boron and lithium, and become an important economic resource. The origin of boron and lithium has long been debated. The aim of this study is to analyze the water chemistry and hydrogen and oxygen isotopic composition of river water to understand the unusual enrichment of boron and lithium in the salt lakes of the Qaidam Basin. Oxygen and hydrogen isotope data show that the source of river water in the winter and summer originates from the Kunlun Mountain ice and snow melt water, respectively. The water chemistry shows that boron and lithium contents are high but little variable with seasons in the Nalenggele River and Wutumeiren River waters. By contrast, other rivers have much lower lithium and boron contents. Moreover, the contents of B3+ and Li+ in the river loads or bed sands show little difference amongst the rivers. This indicates that removal by adsorption or input by surface rock weathering is not the main controlling factor of the B3+ and Li+ variation in the rivers. Rivers with high B3+ and Li+ content are chemically similar to geothermal waters in the Tibetan Plateau. In addition, the source area of the Nalenggele River is located in a collision zone of the Kunlun Mountains and Altun Mountains. Large and deep faults can serve as conduits for geothermal fluids. Thus, deep geothermal waters in the source area can easily migrate to the surface and discharge as springs feeding the rivers. They are an important source of B3+ and Li+ to the rivers. The abnormally high contents of B3+ and Li+ in the Nalenggele and Wutumeiren Rivers also suggest that the geothermal source area may be a future target for boron and lithium resources.

Linear microstability analysis of a low-Z impurity doped tokamak plasma

Improved electron and deuterium energy and particle confinement in the presence of low-Z impurities have been observed in many tokamaks under various experimental conditions. Peaked electron density profiles have been obtained in the Frascati Tokamak Upgrade (FTU) ohmic plasmas where a high concentration of lithium has been detected following the installation of a Liquid Lithium Limiter (LLL). This paper presents the results of a gyrokinetic study on the effects of lithium and other low-Z impurities on the linear stability of deuterium and electron temperature driven modes and their associated fluxes for plasma parameters such as those found in the core of LLL-FTU plasmas.Simulations show that a lithium concentration in excess of nLi/ne = 15%, as estimated in the initial phase of a reference FTU discharge, is found to have a strong stabilizing effect on the TEM and high-frequency ETG modes. A significant stabilization of the electron driven modes can still be observed when the lithium concentration is reduced to 3%.In the presence of a significant impurity concentration (nLi/ne = 3–15%) the long wavelength ITG modes drive an inward electron and deuterium flux and outward lithium flux. This process may lead eventually to an increased electron and deuterium density peaking and a reduced Zeff (lithium density below nLi/ne = 1%).

IRAS 12556–7731: a “chamaeleonic” lithium-rich M-giant

In this letter we characterise IRAS12556-7731 as the first lithium-rich M-type giant. Based on its late spectral type and high lithium content, and because of its proximity in angular distance to the ChamaeleonII star-forming region, the star was misclassified as a young low-mass star in a previous work. Based on HARPS data, synthetic spectral modelling, and proper motions, we derive the astrophysical parameters and kinematics of the star and discuss its evolutionary status. This solar-mass red giant (Teff=3460+/-60K and log(g)=0.6+/-0.2) is characterised by a relatively fast rotation (v sin(i)~8km/s), slightly subsolar metallicity and a high-lithium abundance, A(Li)=2.4+/-0.2dex. We discuss IRAS12556-7731 within the context of other known lithium-rich K-type giants. Because it is close to the tip of the red giant branch, IRAS12556-7731 is the coolest lithium-rich giant known so far, and it is among the least massive and most luminous giants where enhancement of lithium has been detected. Among several possible explanations, we cannot preclude the possibility that the lithium enhancement and rapid rotation of the star were triggered by the engulfment of a brown dwarf or a planet.

Caloric evaporation of the brine in Zangnan Salt Lake

Zangnan Salt Lake on the south of the Tibet is a type of carbonate lake with high concentrations of lithium, boron, and potassium and obviously it differs from seawater in its chemical composition. An experimental simulation of the caloric evaporation of the lake’s brine was conducted by first freezing the brine and then performing isothermal evaporation at 288.15 K. The freezing path and the physicochemical properties of the brine were determined. The crystallization sequence was natron, hydrohalite, halite, sylvite, zabuyelite, trona, aphthitalite, thermonatrite, and borax. Rubidium and cesium salts did not crystallized out but concentrated in the mother solution. The physicochemical properties (density, refractive index, conductivity, and pH) of the liquid phase changed as the evaporation progressed. In the beginning of the evaporation processes, the concentration of potassium ions in the liquid phase gradually increased but later it decreased. A peak value of 55.21 g/L was obtained when the evaporation was 88% complete. When the mineral aphthitalite began to crystallize; the concentrations of B2O3, Li+, Rb+, and Cs+ gradually increased as the evaporation progressed. When the evaporation was 98% complete, their concentrations in the mother liquor were 40.77 g/L, 4.838 g/L, 400.17 mg/L and 31.95 mg/L, respectively. This essential fundamental study can provide an important reference for the comprehensive utilization of brines in Zangnan Salt Lake.

Determination of trace lithium in human erythrocytes by electrothermal atomic-absorption spectrometry with pyrocoated graphite tubes and integrated platform.

Electrothermal graphite-furnace atomic-absorption spectroscopy with pyrocoated graphite tubes, integrated platform and matrix modification was used to determine submicromolar concentrations of trace lithium in human red blood cells. Matrix-matched samples were used to establish calibration curves for concentrations up to 0.58 microM (addition-calibration method) with satisfactory linearity (r2 > 0.99) and intra- and inter-day variability (CV < 11.4%). The median concentration of trace lithium in the cells of 40 healthy Caucasian volunteers devoid of medical or psychiatric history was 0.23 microM (inter-quartile range 0.20-0.30). The levels of trace lithium in the red blood cells correlated (r2 = 0.83) with plasma concentrations (median 0.13 microM, inter-quartile range 0.11-0.19) measured in the same blood sample. Dietary factors (e.g. consumption of lithium-containing mineral water) affected both levels. The red blood cell/plasma lithium ratio had a median value of 1.57 (inter-quartile range 1.16-2.07), implying that trace lithium is accumulated in erythrocytes. This contrasts with most reports of red blood cell/plasma ratio, measured during therapeutic treatment with lithium, for which the average value is 0.5-0.8, albeit for much higher concentrations of lithium (approx. 500-800 microM). The proposed analytical method has the required sensitivity and accuracy for determination of trace lithium in red blood cells and makes it possible to perform epidemiological studies to assess human exposure to environmental lithium in diet and beverages, and inter-individual variations in trans-membrane and renal lithium kinetics at the submicromolar level.

The effect of lithium addition on aluminum-reinforced α-LiAlO 2 matrices for molten carbonate fuel cells

The effect of lithium hydroxide (LiOH) addition as a lithium source is discussed as a way to prevent Li-ion shortages in aluminum-based α-LiAlO 2 matrices of molten carbonate fuel cells. Our results show that the use of LiOH as a lithium source to prevent a Li-ion shortage caused by a lithiated Al-reaction during the operation of the cell allows for more stable performance and greater durability than when lithium carbonate (Li 2CO 3) is used as the lithium source. The behavior of high-lithium content mixtures is attributed to the presence of reactive aluminum particles, which promote the formation of lithium aluminate (LiAlO 2) phases at 650 °C. The incorporation of low-melting-point lithium and an efficient pathway to the aluminum in a reinforced matrix has improved the in-situ mechanical strength via the lithiated Al-reaction, and they do not lead to any noticeable loss in cell performance, even after 4000 h of operation. From the post-test results, the cell with LiOH stored in the cathode channel shows effective formation of the stable crystalline phase of α-LiAlO 2 and enhancement of the mechanical strength during cell operation.

Three-Step Calcination Synthesis of High-Purity Li8ZrO6with CO2Absorption Properties

Li(8)ZrO(6) contains a high lithium content and may bear a great ability of CO(2) absorption, yet the reports about the properties of CO(2) absorption on Li(8)ZrO(6) are few to date for its difficulty in production. In this paper, high-purity Li(8)ZrO(6) is synthesized via a three-step calcination method combined with an effective lithium source and a suitable initial Li/Zr molar ratio. The produced Li(8)ZrO(6) possesses a great CO(2) absorption capacity of about 53.98 wt % at 998 K, which could be well-maintained in a wide range of CO(2) partial pressures of 0.1-1.0 bar although it decreased gradually during the multicycle process of CO(2) absorption-desorption in a 10% CO(2) feed stream because of the high working temperature. These properties imply that Li(8)ZrO(6) may be a new option for high-temperature CO(2) capture applied in industrial processes such as a steam methane reformer.

Lithium Stabilizes the Inward Facing Conformation of Human Serotonin Transporter (hSERT)

According to the alternate access model of transport, a transporter such as hSERT adopts two major conformations: the outward facing conformation and the inward facing conformation. For a functional transporter the distribution of these states in equilibrium (with and without substrate) is unknown. Furthermore it is unclear how this distribution is affected by various parameters such as the temperature, the external and internal ion composition, the membrane potential etc. Here we tested the effect of various external cations such as sodium, lithium and NMDG on the conformational equilibrium. In this study we probed the conformational equilibrium using three different techniques. First we utilized intramolecular FRET measurements. This was done utilizing a construct of hSERT that had been genetically modified to contain a CFT at the N-terminal end and a YFP at the C-terminal end (CSERTY). CSERTY was heterologously expressed in HEK cells and FRET changes upon administration of different external ions were correlated with the data we obtained from binding of a radio-labeled inhibitor of SERT (second technique) as well as with the data we obtained by testing the accessibility of cysteines introduced by site directed mutagenesis to MTS reagents (third technique). Binding was conducted in membranes of HEK cells that stably expressed hSERT and for the accessibility studies we employed hSERT expressed in Xenopus laevis oocytes. In accordance with previous studies we find that external sodium supports the outward facing conformation. However for high external lithium concentrations we have evidence that the prevalent conformation is inward facing.

Optical and electrical properties of lithium doped nickel oxide films deposited by spray pyrolysis onto alumina substrates

Non-doped and lithium doped nickel oxide crystalline films have been prepared onto quartz and crystalline alumina substrates at high substrate temperature (600 °C) by the pneumatic spray pyrolysis process using nickel and lithium acetates as source materials. The structure of all the deposited films was the crystalline cubic phase related to NiO, although this crystalline structure was a little bit stressed for the films with higher lithium concentration. The grain size had values between 60 and 70 nm, almost independently of doping concentration. The non-doped and lithium doped films have an energy band gap of the order of 3.6 eV. Hot point probe results show that all deposited films have a p-type semiconductor behavior. From current–voltage measurements it was observed that the electrical resistivity decreases as the lithium concentration increases, indicating that the doping action of lithium is carried out. The electrical resistivity changed from 10 6 Ω cm for the non-doped films up to 10 2 Ω cm for the films prepared with the highest doping concentration.

High-Level Exposure to Lithium, Boron, Cesium, and Arsenic via Drinking Water in the Andes of Northern Argentina

Elevated concentrations of arsenic in drinking water are common worldwide, however, little is known about the presence of other potentially toxic elements. We analyzed 31 different elements in drinking water collected in San Antonio de los Cobres and five surrounding Andean villages in Argentina, and in urine of the inhabitants, using ICP-MS. Besides confirmation of elevated arsenic concentrations in the drinking water (up to 210 microg/L), we found remarkably high concentrations of lithium (highest 1000 microg/L), cesium (320 microg/L), rubidium (47 microg/L), and boron (5950 microg/L). Similarly elevated concentrations of arsenic, lithium, cesium, and boron were found in urine of the studied women (N=198): village median values ranged from 26 to 266 microg/L of arsenic, 340 to 4550 microg/L of lithium, 34 to 531 microg/L of cesium, and 2980 to 16,560 microg/L of boron. There is an apparent risk of toxic effects of long-term exposure to several of the elements, and studies on associations with adverse human health effects are warranted, particularly considering the combined, life-long exposure. Because of the observed wide range of concentrations, all water sources used for drinking water should be screened for a large number of elements; obviously, this applies to all drinking water sources globally.

Exploring order–disorder structural transitions in the Li–Nb–N–O system: The new antifluorite oxynitride Li 11NbN 4O 2

A systematic exploratory study of the Li–Nb–N–O system at low oxygen and high lithium contents has been performed. As lithium and oxygen increase, an order–disorder transition has been identified using powder neutron diffraction data between Li 16Nb 2N 8O, which crystallizes in an antifluorite-type superstructure with cationic and anionic ordering, and Li 11NbN 4O 2, a new antifluorite-type oxynitride that shows structural disorder. A description of the synthetic conditions required to prepare these phases and their structural characterization is presented.