Li Content Research Articles

Geochemical constraints on the origin of the rare metal mineralization in granite-pegmatite, evidence from three-kilometer scientific drilling core in the Jiajika Li deposit, eastern Tibetan Plateau

Although the metallogenic mechanism of the Jiajika super-large Li deposits in the eastern Tibetan Plateau has been proposed closely linked to development of the Majingzi granite pluton, the petrogenesis and evolutionary linkages between granite–pegmatites and Li mineralization still remain controversial. Here we investigated Li-Nd isotopes together with major and trace elemental data from a 3-km scientific drillcore and surface samples (including the Li-rich/poor pegmatites, the associated two-mica granite and the metasedimentary rocks) to reveal the magmatic evolution and Li-enrichment mechanism of the Jiajika deposit. In the drillcore, the Li-poor pegmatites overall exhibit low Li isotope values (δ7Li = −1.38 ‰ to +1.98 ‰, mean of +0.34 ‰) and low Li contents (67 to 45 ppm), while the Li-rich pegmatites show slightly higher δ7Li values (+0.9 ‰ to +1.1 ‰) and high Li contents (3078 to 6012 ppm). Additionally, the Li-poor pegmatites have εNd(t) values of −17.1 – −2.5 (mean of −10.34) and low Nd concentration (<10 ppm), similar to the two-mica granite (εNd(t)avg = −11.18 and Ndavg = 7.08 ppm), whereas the schists and calc-silicate rocks in the drillcore have relatively higher εNd(t) values (−11.9 to −2.4 with a mean of −7.3) and Nd contents (>20 ppm). These data, together with consistently low Nb/Ta、Zr/Hf of the deep-drilled pegmatites and two-mica granites, suggest that the Jiajika pegmatites are not directly derived from low degrees of partial melting of the Triassic metasediments (e.g., biotite shists or calc-silicate rocks), but more likely from extreme magmatic fractional crystallization of the Majingzi two-mica granite pluton. For the surface samples, the δ7Li values of the surface Li-poor pegmatite samples (−0.61 ‰ to +2.56 ‰ with a mean of +0.36 ‰) are slightly higher than that of the Li-rich pegmatites (−0.52 ‰ to −0.27 ‰ with a mean of −0.39 ‰), and the two-mica granites samples show relatively variation in δ7Li (−1.25 ‰ to +3.33 ‰ with a mean of +0.73 ‰). The surface granites and pegmatites are characterized by high A/CNK values (>1.1) and low K/Rb values (<200), and particularly, the degree of REE tetrad effect gradually increases from granites to pegmatites. We suggest that the Majingzi two-mica granites exposed by the Jiajika gneiss dome is analogous to the deeper granitic sheet implied by the 3 km deep drilling, which both are strongly peraluminous S-type granites with a highly fractionation. Based on the degree of evolution of the Li-rich, Li-poor pegmatites and the two-mica granites and other geochemical evidence, we used a Rayleigh fractionation model to reproduce Li isotope variations in different types of rocks around the Jiajika deposit, suggesting an extreme magmatic differentiation without significant fluid exsolution as the origin for Li enrichments in pegmatites.

Lithium and strontium accumulation in native and invasive plants of the Sava River: Implications for bioindication and phytoremediation

The objective of this study was to investigate the potential of native and invasive plant species for the uptake and accumulation of lithium (Li) and strontium (Sr) along the Sava River, focusing on their bioindication and phytoremediation capabilities. Sampling was carried out in riparian zones exposed to different pollution sources in Slovenia, Croatia, and Serbia. Plant samples of native (Salix alba, Populus alba, Populus nigra, Ulmus glabra, Juglans regia) and invasive (Amorpha fruticosa, Reynoutria japonica, Solidago canadensis, Impatiens glandulifera) species were collected. The content of Li and Sr was analyzed in the soils, roots, and leaves of the selected plants, as well as physical and chemical soil properties. Both Li and Sr content in the soils increased from the source to the mouth of the Sava River. The native species showed significant potential for Li and Sr accumulation based on the metal accumulation index. The highest Sr accumulation was measured in the leaves of Salix alba and the roots of Juglans regia, while the highest Li accumulation was measured in Ulmus glabra. Native species, especially Salix alba, proved to be better bioindicators of Li and Sr. Invasive species, especially Amorpha fruticosa and Impatiens glandulifera, showed a remarkable ability to translocate Sr and Li, respectively, to leaves. These results provide valuable insight into the suitability of plants for biomonitoring soil contamination and potential applications in phytoremediation strategies. In summary, the study shows the importance of native species in the context of the accumulation and bioindication of soil pollution.

(Digital Presentation) Direct Regeneration of NMC622 Cathode Material from Spent EV Li-Ion Batteries Via Hydrothermal Re-Lithiation

With the increasing demand for electric vehicles, there is a need to address the issues associated with the increasing number of waste or spent Li-ion batteries. A simpler and less expensive approach to recycle cathode materials from spent batteries, compared to hydrometallurgy and pyrometallurgy, is direct regeneration. In this study, a facile and cost-effective hydrothermal re-lithiation method, followed by post-annealing, was explored to repair the structure, morphology, and composition of spent NMC622. The effects of annealing temperature and purging gas on the physicochemical properties of the regenerated NMC622 were evaluated. The regenerated NMC622, annealed at 800°C under O2, exhibited an XRD profile that closely resembled that of the as-received spent NMC622, with peaks indexed to the planes of the α-NaFe2O4 structure and without any impurities. Additionally, it achieved the highest I(003)/I(104) ratio and the closest c/3a ratio to that of the as-received spent NMC, indicating that the original structure was successfully repaired after regeneration. It also exhibited less agglomeration, with a narrower particle size distribution than the as-received spent NMC622, indicating that the morphology was improved after regeneration. Elemental composition analyses further confirmed that the spent NMC622 was successfully regenerated using the employed method, as the Li content after regeneration increased from 6.99 to 7.20 wt%, a value close to the theoretical (7.16%). In general, this simple and inexpensive direct regeneration strategy provides a new perspective for lithium-ion battery regeneration, which can be extended to other battery systems in the future.

Synthesis, Structural and Electrochemical Investigation of Disordered Rock Salt Compounds Based on Ni and Ti

Li-ion batteries achieved in the last 3 decades extremely high energy densities, making them the energy storage devices of choice for the electrification of our society. Despite this improvement, their energy density is still low as compared to gasoline, motivating further research towards materials with better performances. State of the art positive electrodes are nowadays layered materials with a ratio Li:M of 1:1, with M being one or multiple transition metals. Disordered rock salt (DRX) materials without a layered structure were thought to be electrochemically inactive. With the development of the percolation theory, 1(Urban, Lee, and Ceder) it was demonstrated that lithium-rich materials (Li:M>1) with a cation disordered rock-salt structure (DRX) can achieve high reversible specific capacities. The general formula of these lithium-rich compounds can be written Li1+y(MM′)1−yO2 where the Li content ranges usually from 1.05 to 1.33, essential to promote Li percolation pathways. With M is indicated a redox active specie (Mn, Ni, Fe, Cr, V) and M’ is typically a d0 element, which is redox inactive during charge and discharge and therefore stabilizes the disordered structure and acting as charge compensator.2 (Chen, Ahn, and Chen)In this work a class of Li-rich compounds with the chemical composition Li2yNiyTi2-3yO2 has been investigated (y = 0.50, 0.55, 0.60, 0.67). These samples were prepared via solid-state reaction at three different temperatures (700 °C, 800 °C, 900 °C). X-ray diffraction has been used to determine the crystal structure of the samples, revealing a predominant rock salt-type phase. However, by decreasing the synthesis temperature and increasing the Li content, phase separation occurs into a rock salt-type and a Li2TiO3 phase. The synthesis has been also verified by DFT and by in situ X-ray diffraction. Neutron diffraction experiment have been carried out to fully understand the cationic distribution in the samples. Finally, the electrochemical performances of the samples have been investigated in Li half cells, revealing a strong voltage hysteresis between charge and discharge.3 (Li et al.) Bibliography Urban, Alexander, Jinhyuk Lee, and Gerbrand Ceder. “The Configurational Space of Rocksalt-Type Oxides for High-Capacity Lithium Battery Electrodes.” Advanced Energy Materials 4, no. 13 (September 2014): 1400478. https://doi.org/10.1002/aenm.201400478.Chen, Dongchang, Juhyeon Ahn, and Guoying Chen. “An Overview of Cation-Disordered Lithium-Excess Rocksalt Cathodes.” ACS Energy Letters, March 17, 2021, 1358–76. https://doi.org/10.1021/acsenergylett.1c00203.Li, Biao, Khagesh Kumar, Indrani Roy, Anatolii V. Morozov, Olga V. Emelyanova, Leiting Zhang, Tuncay Koç, et al. “Capturing Dynamic Ligand-to-Metal Charge Transfer with a Long-Lived Cationic Intermediate for Anionic Redox.” Nature Materials 21, no. 10 (October 2022): 1165–74. https://doi.org/10.1038/s41563-022-01278-2

Battery Electrode-Based Lithium Recovery from Geothermal Brines

Driven by the electrification of transport sector the demand of lithium for battery application is increasing exponentially. The major sources for lithium are continental brines and hard minerals where the production comes along with consumptive water requirements and energy intensive processing and extraction. Therefore, it is of tremendous importance to consider alternative, non-conventional, sources and to develop more efficient and environmentally benign Li extraction methods. Geothermal brines can have significant Li concentrations (150–240 mgLi+ L−1)[1] and could represent an attractive sustainable lithium source. Implementing electrochemical methods for lithium extraction offers further advantages of high Li-selectivity, minimal waste production and low water consumption.[2] Here, we present a dual-ion battery type setup for the selective electrochemical Li-adsorption and desorption from geothermal brines. The chloride concentration in brines is a thousand times higher than that of Li+, hence, both species can be captured at opposite electrode sides. In the dual-ion setup presented in this work, Li+ are stored in a Li-selective LiFePO4(LFP) battery electrode and Cl− are stored using bismuth oxychloride (BiOCl) as counter electrode that has shown excellent Cl− storage capabilities and chemical stability in chloride-ion batteries and desalination batteries.[3] In the second step, both ions are released in a recovery solution to yield a Li-rich solution that could be further processed into battery-grade lithium hydroxide or carbonate. The stability of LFP in aqueous solutions and high Li -selectivity makes it a favored candidate for the electrochemical recovery of Li from natural solutions, where a diverse mixture of cations and anion is present.[4] Therefore, we examined the stability of the electrodes in brine solutions by XRD, indicating good reversibility and no intercalation of competitor ions. In addition, the Li-selectivity in extraction/recovery experiments was analyzed by ICP-OES and influences of different process parameters (e.g. current density, pH, temperature) were investigated. The results demonstrate that the LFP/BiOCl dual-ion battery setup is a feasible and promising low cost method for environmentally friendly Li extraction from geothermal brines.

Tin Mineralization in the Triassic Chacaltaya District (Cordillera Real, Bolivia) Traced by In Situ Chemical and δ18O-δ11B Compositions of Tourmaline

Abstract We present a petrographic and geochemical study of tourmaline from the Triassic Chacaltaya Sn-polymetallic district in the Cordillera Real of Bolivia. Tourmaline is associated with greisens, breccias, and veins, which occur around the Triassic Chacaltaya peraluminous granitic stock hosted by Silurian metasedimentary rocks. Three main petrographic types of hydrothermal tourmaline have been identified: pre-ore greisen-related (Tur-1), syn-ore breccia-related (Tur-2), and syn-ore vein-related (Tur-3). The three types of tourmaline belong to the alkali group and have Fe-rich compositions mostly close to the schorl end member. Overlapping Fe/(Fe + Mg) ratios suggest broadly similar compositions of the hydrothermal fluids during the deposition of tourmaline. The most notable differences in minor and trace element contents include relative enrichment in Zn and Li in Tur-1 and relative enrichment in Ca, Sc, V, Cr, Sr, Sn, Y, Cs, Be, and Zr in Tur-3, with Tur-2 showing intermediate compositions between those of Tur-1 and Tur-3. The progressive enrichment in Sn from Tur-1 (avg = 14 ppm) through Tur-2 (avg = 311 ppm) and Tur-3 (avg = 476 ppm) indicates an increase of Sn concentrations in the hydrothermal system coinciding with cassiterite deposition in breccias and veins. The transition from high Li and Zn contents in Tur-1 to elevated Ca, Sr, V, and Cr contents in Tur-3 is interpreted as reflecting interaction between a hydrothermal fluid of magmatic origin and the metasedimentary country rocks. Strong and relatively steady positive Eu anomalies in all tourmaline types suggest dominantly reduced hydrothermal conditions. In situ δ18O and δ11B analyses of greisen-related Tur-1 reveal crystallization in isotopic equilibrium with magmatic water derived from a peraluminous S-type granite. In contrast, higher δ18O values of breccia-related Tur-2 and vein-related Tur-3 indicate crystallization in isotopic equilibrium with a fluid of metamorphic origin or a magmatic fluid that variably interacted with the metasedimentary host rocks. Geochemical modeling reproduces interactions between a fluid of magmatic origin and the host metasedimentary rocks at moderate water/rock ratios between 0.1 and 0.5. We conclude that cassiterite mineralization in the Chacaltaya district was formed primarily through interaction between B-Sn–rich magmatic fluids and the metasedimentary country rocks.

Enhanced stability of Li metal anodes enabled with iron oxides modified Cu foil

Li metal is widely regarded as the ideal material for anodes in high energy density batteries. Nonetheless, the growth of dendrites and its limited stability significantly hinder the practical use of Li anodes in commercial applications. Herein, we have successfully prepared iron oxides on the Cu current collector by the combination of vacuum evaporation coating and annealing under O2 atmosphere. During the charge/discharge processes, the iron oxides of the oxidized-Fe/Cu foil can react with lithium to generate Li2O, which is beneficial for both the deposition behavior and the ions conduction of Li. Therefore, the oxidized-Fe/Cu foil shows an excellent cycling stability, even when increasing total Li content up to 4 mA h cm−2, the oxidized-Fe/Cu foil can still be steady for 120 cycles. The LiFePO4||oxidized-Fe/Cu-Li full-cell demonstrated improved cycling stability and exceptional rate performance, allowing it to achieve a high specific capacity of 107.7 mA h g−1 at a rate of 10C. This work presents a straightforward approach to creating lithium batteries with extended lifespan and increased capacity.

New Insights into the All-Dry Synthesis of NMC622 Cathodes Using a Single-Phase Rock Salt Oxide Precursor.

In this study, new insights into the all-dry synthesis of the LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode using a single-phase rock-salt (RS) oxide precursor are provided. It was found that use of a larger amount of excess Li content not only can enhance the electrochemical performance of NMC made from the RS-precursor but also increase the degree of homogeneity of the NMC cathode material. In situ XRD analysis showed that lithiation of the RS-precursor (i.e., formation of the O3-phase) starts at a higher synthesis temperature (∼450 °C) than that is required when using a hydroxide precursor (HP) and lithium carbonate (∼350 °C). Consequently, Li2CO3 was consumed by the reaction with the HP at low temperatures before the temperature reached the Li2CO3 melting point. In contrast, the reduced lithiation kinetics of the RS-precursor results in the presence of liquid Li2CO3 during the synthesis, which rapidly increases the rates of precursor lithiation and increases the NMC primary particle size.

Unveiling Oxygen Evolution Reaction on LiCoO2 Cathode: Insights for the Development of High‐Performance Aqueous Lithium‐ion Batteries

AbstractAqueous lithium‐ion batteries (ALIBs) are attracting significant attention as promising candidates for safe and sustainable energy storage systems. This paper delves into the crucial aspects of ALIB technology focusing on the interaction between LiCoO2 (lithium cobalt oxide) cathode material and water electrolytes, with a specific emphasis on the Oxygen Evolution Reaction (OER) process. Fundamental understanding of the electrochemical behavior of LiCoO2 in aqueous electrolytes is crucial for enhancing the performance, safety, and longevity of ALIBs using LiCoO2 as the cathode material.Through a comprehensive periodic density functional analysis of the LiCoO2‐water at the cathode interface, the potential catalytic contributions to the OER mechanism of LiCoO2 are explored. The catalytic properties of LiCoO2 towards OER are investigated considering different steady states of the lowest energy surfaces of LiCoO2 and three different Li concentrations. Our results do not predict the formation of oxygen gas due to the expected large overpotentials, although the exergonic water decomposition to hydroxyl by means the first proton‐electron transfer is predicted at equilibrium potential. This work contributes to the fundamental understanding of LiCoO2 as cathode for aqueous lithium‐ion batteries, reporting the pros and cons of one of the most common cathode materials for traditional non‐aqueous batteries.

Geological controls on lithium production from basinal brines across North America

With increasing lithium (Li) demands for electric car batteries and grid storage, additional Li beyond traditional continental brines and hard-rock sources might be necessary. Elevated Li concentrations have been reported in select oil field brines. Li could be extracted from the large volumes of saline fluids produced by oil and gas wells or from new wells dedicated to Li production. However, the spatial distribution of Li+ concentrations, the rates at which fluids can be produced in areas with elevated Li+ concentrations, and potential sources of Li enrichment are not well characterized. To help identify additional sources of Li, this study investigates the concentration, origin, and potential production rates of Li from sedimentary basin brines across North America. New Li data from brines in various stratigraphic units in the Paradox Basin are combined with existing datasets from the basin and others across North America. New Li analyses of organic-rich shales in the Paradox Basin are also examined to provide insights into the origins of Li. Results from this study show the median Li+ concentration in oil and gas produced waters across North America is ~5 mg/L; these generally low concentrations are unlikely to support Li production. However, higher Li+ concentrations (>65 mg/L) are found in select basins and strata containing deep saline fluids, associated with evaporation of paleo-seawater and precipitation of halite and potash salts, that have not been flushed by meteoric recharge. High Li content of organic-rich shales (range: 20–440 ppm; median: 60 ppm) interbedded with evaporites in the Paradox Basin suggest fluid-rock interactions with diagenetically-altered shales and organic matter are one potential source of Li-enrichment in basinal brines. Observed fluid production and injection rates indicate that Li production will likely be highest in sandstone and carbonate formations with relatively high permeability. Potential Li production rates can vary by orders of magnitude even within these strata due to heterogeneity in both Li concentrations and permeability, as well as recovery efficiencies between 40 and 70 % with current technology. Targeted Li production wells, rather than relying on existing oil and gas wells, would likely be necessary to produce brines at sufficient volumes to support Li production at these low concentrations. Co-recovery of other critical elements or combination with other subsurface developments, such as geothermal energy production, may make Li production from sedimentary basin fluids more viable.

Controlled Li Alloying by Postsynthesis Electrochemical Treatment of Cu2ZnSn(S, Se)4 Absorbers for Solar Cells.

Li-alloying of Cu2ZnSn(S, Se)4 (CZTSSe) absorbers is widely accepted for its beneficial influence on the performance of CZTSSe-based thin film solar cells. Given the degraded morphology characteristic of absorbers synthesized in the presence of excess Li concentrations, it is speculated that Li may be best incorporated into the absorber after synthesis. Here, we report an innovative method to add Li to synthesized CZTSSe by an electrochemical treatment using a liquid electrolyte. Our approach decouples Li addition from absorber synthesis, allowing one to possibly overcome morphology issues associated with high Li concentration. We show that Li is thereby transferred to the absorber and is incorporated into the crystal lattice. The resulting Li concentration in the absorber can be easily controlled by the treatment parameters. Using liquid electrolytes allows a straightforward disassembly of the lithiation setup and hence the fabrication of solar cells after electrochemical treatment. Electrochemically lithiated solar cells reached power conversion efficiencies of up to 9.0%. Further optimization of this innovative method is required to reduce expected interface issues resulting from the electrochemical treatment to demonstrate a gain in the power conversion efficiency of the CZTSSe solar cells. Finally, our results indicate strong lateral Li diffusion, which deserves further investigation. Moreover, the method could be transferred to other material systems, such as Cu(In, Ga)Se2 (CIGS), and adapted to treat layers with other alkali elements such as Na.

Contrasting sources and enrichment mechanisms in lithium-rich salt lakes: A Li-H-O isotopic and geochemical study from northern Tibetan Plateau

Lithium (Li), a crucial mineral resource for modern high-tech industries, is notably abundant in the northern Tibetan Plateau, primarily within lithium-rich salt lakes. However, the exploration and development of these resources are hindered due to an incomplete understanding of their nature and origin. Here we present results from a comprehensive study on the hydrochemical parameters, whole-rock geochemistry, H-O isotopes, and Li concentrations in surface brine, river water, geothermal springs, and associated rocks from two representative lithium-enriched salt lakes, the Laguo Co (LGC) and Cangmu Co (CMC) in Tibet to understand the genetic mechanisms. Our water-salt balance calculations and H-O isotopic analysis reveal that Li in LGC and CMC primarily originates from the Suomei Zangbo (SMZB, ∼91%) and Donglong Zangbo (DLZB, ∼75%) rivers, respectively. It is estimated that the LGC and CMC took a minimum of 6.0 ka and 3.0 ka to accumulate their current lithium resources, respectively. The distinct geological characteristics reflect evolutionary differences between the two lakes, suggesting diverse lithium sources and enrichment processes. The high lithium ion concentration and light lithium isotope composition in the SMZB river waters indicate the genetic relationship with lithium-enriched geothermal springs in the Tibetan Plateau. Our results suggest that lithium in the LGC originates from lithium-enriched geothermal springs and is primarily supplied through the small-scale SMZB river. In contrast, the formation and evolution of CMC are influenced by the northern Lunggar rifts, receiving a prolonged and stable input from the DLZB, resulting in high lithium concentrations and isotopic values. The absence of lithium-enriched geothermal springs and the prevalence of silicate rocks in the CMC catchment suggest that lithium may be sourced from the weathering of silicate rocks, such as granitic pegmatite veins containing lithium-rich beryl, widely distributed in the upstream area of DLZB. The forward modeling approach, quantifying the contribution fractions of different reservoirs (atmospheric precipitation, silicate, carbonate, and evaporite), indicates that the distinct lithium concentrations in the mainstream (>1 mg/L) and tributaries (<0.1 mg/L) are positively correlated with the ratio of silicate contributions to carbonate contributions, suggesting that dissolved lithium in river waters primarily originates from the weathering and dissolution of silicate rocks. The distinct sources and enrichment mechanisms of lithium in these two salt lakes are attributed to various evolutionary processes, topographical features, hydrological factors, fundamental geological settings, and tectonic histories, despite their spatial proximity. Furthermore, our study highlights the significant role of rivers in the formation of young salt lakes, in addition to geothermal springs.

LiGaSiO4: An ultra-low permittivity dielectric material enabling application in patch antenna

A low permittivity microwave dielectric ceramic, Li-containing silicate (LiGaSiO4), was synthesized using the standard solid-state reaction method. The nominal LiGaSiO4 ceramic exhibited a relative permittivity of approximately 4.4. The effects of nonstoichiometric Li on the microstructure, sintering behavior, and microwave dielectric properties of LiGaSiO4 were comprehensively investigated. Excess Li content (6 mol%) significantly improved the relative density (96.1 %) and microwave dielectric properties (εr∼5.34, Q × f ∼55,600 GHz, and τf ∼ -48.6 ppm/°C), while reducing the optimum sintering temperature from 1070 °C to ∼1010 °C. Additionally, the incorporation of 2 wt% LiF further reduced densification temperature (∼940 °C). The regulation of the τf was achieved through the addition of CaTiO3 ceramic, and a patch antenna was designed and fabricated using a modified Li1.06GaSiO4-LiF-CaTiO3 composite ceramic. The resulting patch antenna resonates at 5.87 GHz with an impressive bandwidth of 83.1 MHz, while both simulated and measured results demonstrate excellent agreement.

Isotopic evolutionary track of water due to interaction with rocks and its use for tracing water cycle through the lithosphere

Hydrogen and oxygen isotopic compositions of natural spa waters from hot and/or mineral-rich springs (including flowing/pumping wells) potentially provide important clues about water cycle in Earth's interior, because some of the waters are deep-seated and non-meteoric. However, the isotopic compositions of these waters are typically altered by contamination with meteoric water and are thus poorly known. To reconstruct their original (i.e., before these waters mix with meteoric water) isotope compositions, here we develop an isotopic evolution model of the lithosphere-enclosed waters and derive the “ocean-origin lithospheric water curve” (OLWC; δ2H = 60 / (δ18O – 11)) as a typical evolutionary track starting from ocean water. Then we apply them to spa waters from central Japan, a globally unique geotectonic region where double subduction of slabs occurs. The OLWC explains well observed isotope data of subseafloor pore waters, submarine mud volcano pore waters, coastal oil-field brines, and subduction zone volcanic steam. Mixing analysis indicates that lithospheric water accounts for 19–95 % of each spa water we investigated. The nonlinear relationships of the reconstructed water δ18O and Cl or Li concentrations justify our hypothesis that the lithospheric waters are undergoing evolution from ocean water to magmatic water by rock-water isotopic exchange and that they are not simply mixtures of the two. A comparison of the reconstruction results with model predictions under slab subduction settings suggests that most spa waters in the southern to central part of the study region contain progressively evolving lithospheric waters released from the subducting Philippine Sea slab, and that a few at western edge of the region contain waters released from the Pacific slab. The others in the northern and eastern part of the region contain waters at the early-to-mid evolutionary stage, which are discharged from Tertiary marine sedimentary rocks (including tuffs). All these waters were enclosed in the lithosphere for more than 1–5 Ma. Our approach provides useful tools for tracing sources of non-meteoric water and highlights water cycle through lithosphere for more than one million years.

Microstructural evolution and hydrogen content and their effect on properties of TiB2/Al-Li-X composites with different Li contents

The content and proportions of the major solute elements in aluminum matrix composites are critical to the microstructure and properties of the material. This paper uses a stepwise method based on ultrasonic in-situ casting technology to prepare TiB2/Al-Li-X composites with different Li contents (0.5–3.0 wt%). The composites' microstructure morphology, precipitates, hydrogen content, and mechanical properties were tested and analyzed. The results showed that with the increase of Li content, the number of θ′ phases decreases, the number of δ′ phases increases, while the number of T1 phases increases and then decreases, and the TiB2 particles promote the precipitation of T1 phases at low Li content; meanwhile, the hydrogen content keeps increasing, and the grain size decreases and then increases. The increase of the T1 phase and the decrease of grain size enhance the strength of the composites, while the increase of δ′ phase and hydrogen content increase the hardness but decrease the plasticity. When the Li content is around 1.5 wt%, the grain size is minimized, the TiB2 particles are fine and dispersed, the yield strength reaches the maximum value of 166.9 MPa, and the mechanical properties are relatively balanced.

Controls on lithium content of oilfield waters in Texas and neighboring states (USA)

The amount of lithium (Li) required to support the energy transition underscores the need to develop Li sources beyond the traditional hard-rock mining and surface continental brines. The objective of this study was to explore the potential for Li production from oilfield waters in the U.S. Gulf Coast region. Data on Li concentrations were obtained from ~2450 formation water samples taken in states along the greater Gulf Coast (NM, TX, OK, LA, AR, and MS). The dataset contains geochemical analyses that spans >70 years, including the USGS database (v2.3), compilation of recent data previously published by the authors, analyses from recently collected samples and from archived samples, and data from U.S. Bureau of Mines reports.Aqueous Li distribution is lognormal, typical of trace elements, with background levels in the 0–20 mg/L range. High concentrations (≥80 mg/L) are restricted to some intervals at certain locations: Jurassic Smackover Formation, a well-known brine deposit in Arkansas (300+ mg/L Li), but also along the Gulf Coast in Texas, Louisiana, and Mississippi (several samples ≥100 mg/L Li); Permian and Pennsylvanian Granite Wash in the Anadarko Basin of Texas (several samples >100 mg/L Li) (not confirmed); and Cretaceous Edwards Formation of South Texas (several samples ≥100 mg/L Li). Genetic models for Li enrichment are lacking, but high Li seems to be related to the noted fact that Li concentrations increase with depth and with total dissolved solids. Other common characteristics of high-Li brines in the Gulf Coast are high K, Ca, and B, which reflect water-rock interactions, presence of major faults, and association with higher permeability intervals that can spread Li-bearing fluids. Host rocks for high-dissolved Li brines commonly are carbonates, possibly because of their limited sorption opportunities. Close connection to an igneous basement or to a depositional environment that supported accumulation of surface continental brines does not seem to be required.

Distribution and enrichment of rare metal elements in the basement rocks of South China: Controls on rare-metal mineralization

The southeastern part of the South China Block (SCB) is composed of the Nanling-Yunkai and Wuyi terranes and the Jiangnan Orogenic Belt (JOB), of which the Nanling and the JOB are two world-famous rare-metal metallogenic belts. Rare-metal deposits in both areas are closely associated with crustally-derived granites. However, rare-metal abundances and enrichment mechanisms in Precambrian basement rocks, which probably are sources of the ore-forming granites in the SCB, have not been well understood. Bulk compositions of more than 800 basement rock samples are used to unravel the abundances, variation and enrichment mechanism of the rare-metal elements in Precambrian basement rocks of the SCB and their genetic links with rare-metal mineralization. The basement meta-sedimentary rocks of the westernmost section of the JOB have the highest Sn (10.2 ppm), W (7.7 ppm), Be (3.46 ppm) and Cs (17.1 ppm) abundances, whereas those of the eastern JOB have low Sn (2.4–3.2 ppm), W (1.2–2.1 ppm), Nb (12.9–13.9 ppm) and Be (2.22–2.34 ppm), but relatively high Li (53.3–57.0 ppm) contents. The eastern Nanling basement rocks show high Sn (4.5 ppm), W (3.0 ppm) and U (3.67 ppm) relative to upper continental crust (UCC), similar to the western Nanling basements (4.2 ppm, 3.0 ppm and 4.03 ppm, respectively), but have significantly higher Rb/Sr, Li, Be, Cs and lower CaO/Na2O and Ba than the western Nanling basements, implying the presence of more meta-pelitic rocks in the eastern Nanling basements. The Wuyi terrane is characterized by low rare-metal abundances, e.g Sn (2.1 ppm), W (1.3 ppm), Cs (5.7 ppm) and Li (36.4 ppm). Rare-metal enrichment mechanisms are also distinct in the basement rocks of different terranes of the SCB. Four types of enrichment mechanism are identified: magmatic recycling, chemical weathering, source enrichment and alternative redox depositional environments. The enrichment of Sn, W, Cs and Be in the westernmost basement of the JOB is attributed to a higher proportion of old and multi-cycled materials and alternating depositional environments, and the enrichment of Sn, W, REE and U in the Nanling basement is ascribed to the higher proportion of recycled detritus and an enriched source. Chemical weathering (clay adsorption) is an important initial enrichment mechanism in the eastern JOB basement. Comparisons of rare-metal mineralization in the SCB with the basement compositions suggest that rare-metal mineralization of the granites is not only related to the rare-metal contents of the source, but also is closely related to the lithology of the source. Stronger W mineralization in the eastern JOB and eastern Nanling than in their western parts is probably related to their more pelite-rich basements.

Conversion of Aluminosilicate Residue Generated from Lithium Extraction Process to NaX Zeolite

The production of lithium from spodumene ores generates huge amounts of residues mainly composed of aluminosilicates. The main objective of the present study was to synthesize NaX zeolites with good ion-exchange capacity from these aluminosilicate residues, without using the fusion step or chemically modifying their initial Si/Al ratio. A physico-chemical (chemical composition, sorption capacity) and mineralogical (XRD, SEM) characterization of the zeolite synthesized using the conventional hydrothermal process (Process_1) was performed and compared with zeolite produced using a fusion step followed by a hydrothermal treatment process (Process_2) and commercial zeolite 13X. Then, the effect of operating parameters such as aging time and temperature, crystallization time and solid/liquid ratio on the sorption capacities of the synthesized zeolites using the conventional hydrothermal process was assessed. Initial aluminosilicate residues were mainly composed of Al2O3 (24.6%) and SiO2 (74.0%), while containing low amounts of potential contaminants (&lt;1.6%). Based on its chemical composition, the fine fraction (&lt;53 µm) was identified as the most suitable fraction to produce zeolites, while coarser fractions which contained higher Li content can be used to produce glass and ceramics. Physico-chemical and mineralogical characterization results show that zeolite produced using the conventional hydrothermal process (Process_1) had similar properties compared to zeolites 13X. Therefore, Process_1 was identified as the most performant while reducing operating costs related to alkaline fusion pre-treatments, which did not significantly improve zeolite properties. Finally, the optimum conditions for converting the residues into zeolite NaX, which had an ion-exchange capacity of 58 mg Ca/g were 8 h of aging at 75 °C and 16 h of crystallization at 100 °C, with a solid/liquid ratio of 1/10 (w/v).

Nanocomposite Li- and Mn-rich spinel cathodes characterized with a green, aqueous binder system

There is a growing need for alternatives to commercialized high-energy–density cathodes for Li-ion batteries with chemistries less dependent on Co and Ni and, in the past decade, particular attention has been placed on Li- and Mn- rich cathodes. Herein we report synthesis and characterization of Li- and Mn-rich cathode active materials (CAMs) with spinel-based nanocomposite structure having stoichiometries LixMn1.5Ni0.5O4 (x = 0.45–1.50) synthesized via liquid-feed flame spray pyrolysis. When cycled from 4.9 to 2.4 V, LixMn1.5Ni0.5O4 (x = 1.26, 1.50) exhibited energy densities greater than 1000 Wh kgCAM-1 using a green, aqueous binder system. Increasing initial Li content results in larger 1st charge capacity, which can potentially serve as a Li donor to irreversible, Li-consuming solid electrolyte interphase formation in next generation anode active materials.

Geochemical features of lithium–rich bauxite from the Benxi Formation in Qinyuan County, Shanxi, China: Insights into their depositional environment and lithium enrichment

Most bauxites in China are the karst type, which usually enriches lithium (Li) resources. Therefore, Li mineralization theory must be further developed to realize the comprehensive utilization of bauxite resources. The Qinyuan Li–rich bauxite is formed in the Benxi Epoch of the Late Carboniferous and its parent rock is the underlying Ordovician limestone. In this study, the methods of stepwise extraction and element geochemical are utilized to discuss the occurrence state and sedimentary environment of Li in Qinyuan bauxite, respectively. Based on the differences in element composition, the Qinyuan Li–rich bauxite sequence can be divided into clay rocks, bauxitic clays, iron–rich clays, and bauxite from the bottom to the top. The Li content of the Qinyuan bauxite samples is highest in clay rocks (averaging 431 µg/g), followed by bauxitic clays (averaging 288 µg/g), bauxite (averaging 252 µg/g), and iron–rich clays (averaging 202 µg/g). The main mineral compositions of these samples are diaspore, calcite, anatase, pyrite, siderite, kaolinite, and illite. Among them, the Li content is positively correlated with clay mineral contents (R2 = 0.71), indicating that clay minerals are the main Li–rich minerals. More specifically, the clay mineral in bauxitic clays, bauxite, and iron–rich clays are kaolinite, and the positive correlation between Li and kaolinite (R2 = 0.46) indicates that kaolinite is the main Li–rich mineral. Nevertheless, the clay minerals in clay rocks are kaolinite and illite, and the correlation between Li and illite (R2 = 0.54) is higher than kaolinite (R2 = 0.10), indicating that Li is preferentially enriched in illite when kaolinite and illite coexist. It was found that the majority (higher than 99 %) of Li is hosted in the vacant sites of Si–O tetrahedral layers and the Al–O dioctahedral layers of illite and kaolinite to compensate the positive charge deficit caused by replacement of Si4+ and Al3+ in the tetrahedral and dioctahedral layers of clay minerals, respectively. Furthermore, the content ratios between typical elements with varied migration–deposition properties can indicate the depositional environment of Li–rich bauxite. Among them, MgO/Al2O3 and Rb/K (range from1.3 × 10-3 to 7.36 × 10-2 and 3 × 10-4 to 3.44 × 10-2 in samples, respectively) can indicate sedimentary environment. Th/U, V/Cr, and V/(V + Ni) (range from 0.45 to 3.73, 0.85 to 3.54, and 0.27 to 0.89 in samples, respectively) can indicate the paleo–redox conditions. Sr/Cu, CIA, and Cvalue (range from3.53 to 48.2, 93.8 to 99.9, and 0.43 to 7.29 in samples, respectively) can indicate paleoclimate. The results show that the Qinyuan bauxite possibly formed in the hot, humid (Sr/Cu > 5, CIA = 85–100, and Cvalue > 0.8), and dysoxic–anoxic (Th/U = 2–7, V/Cr = 2–4.25, and V/(V + Ni) = 0.46–0.84) marine–continental transitional (MgO/Al2O3 = 0.01–0.1 and Rb/K = 4 × 10-3–6 × 10-3) environment.