Li Content Research Articles

Nutritional Value of Coloured Flesh Potato Tubers in Terms of Their Micronutrient Content

The aim of this study was to compare Fe, Zn, Mn, Al and Li contents in table potato tubers, obtained from seven potato cultivars with different flesh colour, and one cultivar characterised by light-coloured flesh. The study material consisted of potato tubers produced in a one-factor field experiment carried out at the Agricultural Experimental Station in Zawady belonging to the University of Siedlce, Poland (52°03′ N, 22°33′ E) in 2021–2023. The following cultivars were tested: Eurostar (light yellow flesh), Rote Emmalie and Herbie 26 (red flesh), Provita, Salad Blue, Blaue Annelise, Vitelotte Noire and Bora Valley (purple and blue flesh). The study showed that the genetic characteristics of the cultivars determined the nutrient content and uptake with tuber yield. Of the tested minerals which are important for human nutrition (Fe, Zn, Mn), red and purple cultivars accumulated more Fe than the light yellow-fleshed Eurostar. Zn content was the highest in red-fleshed cultivars compared with light and purple-fleshed cultivars. Mn content was the highest in the tubers of the light yellow-fleshed Eurostar and lowest in red Rote Emmalie. Fe, Zn, Mn and Al contents and uptake with tuber yield were influenced by weather conditions during the growing season.

Direct Lithium Extraction from α-Spodumene through Solid-State Reactions for Sustainable Li2CO3 Production.

With increasing battery demand comes a need for diversified Li sources beyond brines. Among all Li-bearing minerals, spodumene is most often used for its high Li content and natural abundance. However, the traditional approach to process spodumene is costly and energy-intensive, requiring the mineral be transformed from its natural α to β phase at >1000 °C. Acid leaching is then applied, followed by neutralization to precipitate Li2CO3. In this work, we report an alternative method to extract Li directly from α-spodumene, which is performed at lower temperatures and avoids the use of acids. It is shown that Li2CO3 is formed with >90% yield at 750 °C by reacting α-spodumene with Na2CO3 and Al2O3. The addition of Al2O3 is critical to reduce the amount of Li2SiO3 that forms when only Na2CO3 is used, instead providing increased thermodynamic driving force to form NaAlSiO4 and Li2CO3 as the sole products. We find that this reaction is most effective at 4 h, after which volatility limits the yield. Following its extraction, Li2CO3 can be isolated by washing the sample using deionized water. This energy-saving and acid-free route to obtain Li2CO3 directly from spodumene can help meet the growing demand for Li.

Crystallization Sequence of the Spodumene-Rich Alijó Pegmatite (Northern Portugal) and Related Metasomatism on Its Host Rock

The Barroso–Alvão region is an excellent setting for studying Li mineralization associated with granitic pegmatites and developing Li exploration techniques. Among the distinguished pegmatite types in this pegmatite field, the spodumene-bearing dyke from Alijó is a representative example of an Iberian Li–Cs–Ta (LCT) pegmatite currently under exploitation. In this work, we examine the internal evolution of the Alijó dyke and its external metasomatic effect on the surrounding metasediments, contributing to lithium exploration techniques. Electron microprobe analyses provided clues about the crystallization conditions and the degree of differentiation of the pegmatitic melt, whereas the external metasomatism induced by the spodumene-bearing pegmatite was studied through whole-rock geochemistry. The obtained results indicate that the primary crystallization of the studied dyke likely occurred at temperatures between 450–500 °C, with emplacement at shallow crustal levels of about 2–3 kbar. The high concentrations of trace elements such as Li, Cs, Rb, Be, Sn, Nb, Ta, Ge, U, and Tl in the pegmatitic melt suggests high availability of these elements, allowing their partitioning into an early exsolved fluid phase. The exsolution of this fluid phase, subtracting components such as F and B, from the pegmatitic melt would cause a significant undercooling of the melt. Moreover, the interaction of this expelled fluid with the country rock generated a metasomatic overprint in the surrounding metasedimentary host rocks. The metasomatic effect in Alijó is strongly influenced by the nature of the host metasediments, with a significantly higher grade of metasomatism observed in pelitic (mica-rich) samples compared to psammitic (mica-poor) samples collected at same distances from the dyke. The greisen developed close to the pegmatite contact reflects this metasomatic signature, characterized by the mobilization of at least B, F, Li, Rb, Cs, Sn, Be, Nb, Ta, and Tl. We cautiously suggest that whole rock Li concentrations greater than 300 ppm, combined with a minimum value of 1000 ppm for the sum of B, F, Li, Rb, Cs, and Sn in pelitic metasediments of Barroso–Alvão, may be indicative of a mineralized pegmatite in this region.

Utica/Point Pleasant brine isotopic compositions (δ7Li, δ11B, δ138Ba) elucidate mechanisms of lithium enrichment in the Appalachian Basin

Global Li production will require a ∼500 % increase to meet 2050 projected energy storage demands. One potential source is oil and gas wastewater (i.e., produced water or brine), which naturally has high total dissolved solids (TDS) concentrations, that can also be enriched in Li (>100 mg/L). Understanding the sources and mechanisms responsible for high naturally-occurring Li concentrations can aid in efficient targeting of these brines. The isotopic composition (δ7Li, δ11B, δ138Ba) of produced water and core samples from the Utica Shale and Point Pleasant Formation (UPP) in the Appalachian Basin, USA indicates that depth-dependent thermal maturity and water-rock interaction, including diagenetic clay mineral transformations, likely control Li concentrations. A survey of Li content in produced waters throughout the USA indicates that Appalachian Basin brines from the Marcellus Shale to the UPP have the potential for economic resource recovery.

Effect of Li Doping on Structural, Optical, and Optoelectrical Characteristics of ZnSnO3 Thin Films Prepared by Nebulizer Spray Pyrolysis

In this work, ZnSnO3 (ZTO3) and Li-doped ZTO3 thin films were synthesized on glass slides by a cost-effective nebulizer spray pyrolysis procedure. The X-ray diffraction analysis revealed that the ZTO3 and Li-doped ZTO3 thin films possessed a rhombohedral structure. The structural indices (grain size, dislocation density, lattice strain) of the ZTO3 and Li-doped ZTO3 thin films were computed. The morphology characteristics of the ZTO3 and Li-doped ZTO3 thin films were observed by field emission scanning electron microscopy. The inspected films display uniform and homogeneous surfaces. The optical transmittance, T, and reflectance, R, of the ZTO3 and Li-doped ZTO3 thin films were recorded using a double-beam spectrophotometer to investigate the optical characteristics of these layers. The refractive index of the ZTO3 and Li-doped ZTO3 thin films was enhanced via the Li content increase. Moreover, Tauc’s plots demonstrated that the energy gap of the ZTO3 and Li-doped ZTO3 thin films was reduced from 3.85 eV to 3.08 eV by boosting the Li doping content. Moreover, the increase in Li content produces an enhancement in the optoelectrical indices (optical resistivity, optical carrier concentration, optical mobility, plasms frequency, and optical conductivity) of the ZTO3 and Li-doped ZTO3 thin films. The nonlinear optical indices of the ZTO3 and Li-doped ZTO3 thin films were deduced, and it was noted that Li content boosted the nonlinear optical indices of these layers. All the ZTO3 and Li-doped ZTO3 thin films displayed n-type semiconducting properties by the hot probe equipment.

Li-mineralized pegmatite of anatectic origin: Constraints from Li[sbnd]Hf isotopes and geochemical modeling

Pegmatites are important reservoirs of lithium resources. There is an ongoing debate as to whether Li-mineralized pegmatites were generated from evolved granitic systems via extreme differentiation or by direct melting of metasedimentary rocks. The Chinese Altay is one of the largest pegmatite provinces in the world, and includes many rare-metal pegmatites (e.g., Koktokay, Kelumute, Kaluan and Azubai). However, they display significant differences in formation ages and isotopic compositions compared with the neighbouring or potential parental granites. In this contribution, we present a case study of the Kaluan Li ore deposit in the Chinese Altay, elucidating the origins of pegmatites and related Li mineralization. The Kaluan Li-mineralized pegmatites are characterized by high SiO2, K2O, Na2O, Li, Cs, Ta, and Rb contents; low Fe2O3T, MgO, Ba, and Sr contents; and peraluminous signatures. They have homogeneous HfLi isotopic compositions (εHf (t) = −0.6 to +2.5; δ7Li = +1.6 to +5.8‰) that are within the range of HfLi isotopic compositions of the Kulumuti Group schists (εHf (t) = −2.8 to +7.5; δ7Li = −8.6 to +10.8‰). In addition, the chemical compositions of the melt derived from the partial melting of the Kulumuti Group by phase equilibrium modeling are compatible with our analyses of the Kaluan Li-mineralized pegmatites. These similarities suggest that the Kaluan Li-mineralized pegmatites were derived from the partial melting of the Kulumuti Group schists at depths during the Triassic, in a post-orogenic and extensional setting. The generation of these pegmatites was mostly controlled by biotite dehydration melting at relatively high temperatures, rather than by the low-temperature melting of muscovite. Trace elements modeling results show that approximately 33–36% partial melting of the average Kulumuti Group schist may produce melts with maximum Li concentrations ranging from 664 to 751 ppm. Subsequently, a high degree of fractionation exceeding 85%, was required for the Li concentration of the residual melt to reach concentrations suitable for crystallization into albite-spodumene pegmatites. Based on our research, an anatectic origin model may have general applicability in explaining the genesis and mineralization of rare-metal pegmatites in the Chinese Altay.

Quartz texture and the chemical composition fingerprint of ore-forming fluid evolution at the Bilihe porphyry Au deposit, NE China

Abstract Quartz is widely distributed in various magmatic-hydrothermal systems and shows variable textures and trace element contents in multiple generations, enabling quartz to serve as a robust tracer for monitoring hydrothermal fluid evolution. This study demonstrates that integrated high-resolution SEM-CL textures and trace element data of quartz can be used to constrain physicochemical fluid conditions and trace the genesis of quartz in porphyry ore-forming systems. The Bilihe deposit is a gold-only porphyry deposit located in the Central Asian orogenic belt, NE China. Four quartz generations were distinguished following a temporal sequence from early-stage dendritic quartz, unidirectional solidification textured quartz (UST quartz), gray banded vein quartz (BQ), to late-stage white calcite vein quartz (CQ), with the Au precipitation being mostly related to dendritic quartz, UST quartz, and BQ. The well-preserved dendritic quartz with sector-zoned CL intensities and euhedral oscillatory growth zones crystallized rapidly during the late magmatic stage. The relatively low Al contents of dendritic quartz were interpreted to be related to contemporaneous feldspar or mica crystallization, while the high-Ti contents indicate high-crystallization temperatures (~750 °C). The comb-layered UST quartz displays heterogeneous, patchy luminescence with weak zoning, hosts coeval melt and fluid inclusions, and retains the chemical characteristics of magmatic dendritic quartz. High-Ti and low-Al contents of UST quartz suggest a formation at relatively high temperatures (~700 °C) and high-pH conditions. Three sub-types can be defined for hydrothermal BQ (BQ1, BQ2, and BQ3) based on contrasting CL features and trace element contents. The Al contents increase from BQ1 to BQ2 followed by a drop in BQ3, corresponding to an initial decrease and subsequent increase in fluid acidity. Temperature estimates of BQ decrease from BQ1 (635 °C) to BQ3 (575 °C), which may, however, be disturbed by high growth rates and/or high-TiO2 activities. The CQ typically displays a CL-bright core and CL-dark rim with oscillating CL intensities and is characterized by the lowest Ti and highest Al, Li, and Sb contents compared to the other quartz types, which suggests a deposition from more acidic and lower temperature fluids (~250 °C). Trace element patterns indicate that a coupled Si4+ ↔ (Al3+) + (K+) element exchange vector is applicable to dendritic quartz, UST quartz, and BQ. By contrast, charge-compensated cation substitution of Si4+ ↔ (Al3+, Sb3+) + (Li+, Rb+) is favored for CQ. The comparison with compiled trace element data of quartz from other porphyry Au, Cu, and Mo deposits worldwide suggests that Ti, Al, Li, K, and Ge concentrations, as well as Al/Ti and Ge/Ti ratios, have the potential to discriminate the metal fertility of porphyry mineralization.

Alkali Trace Elements Observed by MarSCoDe LIBS at Zhurong Landing Site on Mars: Quantitative Analysis and Its Geological Implications

AbstractMars Surface Composition Detector (MarSCoDe) is one of the important payloads carried by the Zhurong rover, China's first Mars exploration mission Tianwen‐1. The laser‐induced breakdown spectroscopy (LIBS) instrument of MarSCoDe is mainly used to detect major and trace elements on the surface of Mars. The quantitative analysis of alkali trace elements, namely lithium (Li), strontium (Sr), and rubidium (Rb), holds significance in unraveling the geological evolution of the Zhurong landing site. This study focuses on establishing univariate calibration models using MarSCoDe LIBS spectra from 84 samples tested in the ground laboratory. The accuracy of these models, within a few parts per million (ppm), was subsequently validated through the analysis of 12 onboard MarSCoDe Calibration Targets (MCCTs). With these models, Li, Sr, and Rb concentrations in the surface targets during the initial 300 sols (Martian days) traverse were determined. These concentrations ranged from 6 to 18, 106–628, and 22–87 ppm, respectively. Our results suggest that Li, Sr, and Rb are mainly related to the igneous rock components in the rocks and soils at the Zhurong landing site. The major secondary minerals in MarSCoDe scientific targets are likely small amounts of sulfates, which appear to have formed from the acidic weathering of recent surface brine. Clay minerals are likely either absent or very sparse in the scientific targets. The surface igneous materials at the landing site likely have originated from the most recent lava flow during the Amazonian epoch.

Anatomy and genesis of the world’s largest carbonate-hosted Zn-Pb deposit: New insights from ore characteristics, Zn-Pb-C-O isotopes, and trace element constraints of the Huoshaoyun deposit, Karakorum Range, Xinjiang

The Huoshaoyun deposit in the Karakorum area of NW China is the world’s largest zinc-lead carbonate ore deposit. Here we investigate the genesis of the mineralization based on multiproxy investigations. The deposit contains zinc-lead carbonate and sulfide minerals, with smithsonite (Smt), cerussite (Cer), and sulfides accounting for 85%, 10%, and 5% of the total lead and zinc resources, respectively. Three ore-forming stages, involving Smt, Cer, and sulfides ores were summarized. The Smt mineralization is characterized by veined, massive, and stratified Smt forming horizontal sedimentary layered ore and vertical feeder veins similar to the SEDEX-type deposits. The sulfide and Cer veins display typical hydrothermal characteristics and are superimposed on the massive Smt ores. The Smt ores show high Li, Be, Cr, Y, Ba, Nd, Yb, and Zr contents, whereas the Cer veins have extremely high Sr contents (up to 3814–9174 ppm) and low Zr contents (less than 0.01 ppm). Galena and sphalerite show higher Cd concentrations compared to Smt and Cer ores.The Smt ores differ with different spatial locations, with Smt ores formed at the vent have δ66Zn values of +0.15‰ to +0.21‰, the massive Smt formed close to the vent show a value of +0.13‰, and those formed away from the vent show a value of 0.05‰, all values being close to 0. The sulfides have δ66Zn values of −0.09‰ to +0.04‰. The C-O isotopes of Smt ores are similar to both altered and unaltered host limestone, suggesting that the limestone was a potential source for carbon and oxygen. Quartz with veined Smt shows magmatic signatures with δ18OVSMOW of +1.14‰ to +2.23‰, high Pb (115–401 ppm) and Zn concentrations (390–997 ppm), whereas quartz associated with sulfide has meteoric fluid signature with the lowest δ18OVSMOW (−14‰ to −10.7‰), low Pb (11.6–49.0 ppm) and Zn (18.1–72.8 ppm) concentrations. The temperature of equilibration computed based on oxygen isotope fractionation between Smt and coeval quartz indicate a dual source with that of quartz derived from an aqueous fluid, whereas the source for Smt might involve CO2 or HCO3−.We trace multiple metallogenic stages for this deposit including exhalation, hydrothermal deposition, and fault-controlled sulfide vein formation. The largest orebody (III-1) preserves a 16 Mt reserve of Zn and was formed by crust-mantle interaction at ca. 195 Ma in the early development of the Linjitang post-arc rift system. Fluid convection, zinc enrichment driven by granitic magma, volcanic activity, and karst alteration induced by acid rain in a lagoonal environment promoted ore enrichment.

Analysis of the Concentration of Selected Elements in Teeth Hard Tissues and Their Role in Biomineralization Processes

The role of trace elements, heavy metals, and their effect on the development of hard tissue mineralization balance is poorly documented and the available results are often contradictory. The aim of the present study was the assessment of the concentration of the selected elements in the teeth of deer (Capreolus capreolus) and red deer (Cervus elaphus) with respect to their potential role in maintaining biomineralization balance in teeth hard tissues. Moreover, the aim was to determine whether trace elements accumulate in teeth with age. This study was conducted on 22 molar teeth of red deer (Cervus elaphus) and 54 molar teeth of roe deer (Capreolus capreolus) from Poland. Samples were analyzed with the use of inductively coupled plasma optical emission spectrometry equipped with a concentric nebulizer and cyclonic spray chamber in order to determine their Al, Ba, Cd, Fe, K, Li, Mg, Na, Ni, Pb, Sr, and Zn contents. There were strong positive correlations between strontium and zinc with heavy metals, particularly in dentine, which may affect the neutralization of the negative effects of heavy metals on tooth tissue and, consequently, maintaining ionic balance. The accumulation of trace elements with age in serenades has not been confirmed.

From wide band gap semiconductor to visible light responsive material: The role of Li in K2PdO2

The study used Density Functional Theory (DFT) first-principles calculations to analyze the impact of lithium insertion on K2PdO2, a wide band gap semiconductor with limited absorption in visible electromagnetic radiation. The results showed that Li insertion is a promising method to enhance the absorption behavior of these materials. Both pristine and doped compounds displayed negative formation energies, confirming their structural and thermodynamic stability. The electronic band structure and Density of States plots indicated the semiconducting nature of all three compounds, with the band gap decreasing from 2.29 eV to 1.69 eV upon doping. The rise in refractive index with increasing Li content indicates an increase in charge, leading to polarization and reduced light velocity. Optical conductivity increased beyond the band gap values, indicating the material’s responsiveness to visible electromagnetic radiation. Moreover, the thermoelectric response makes K2PdO2 as best candidate for different thermoelectric devices.

Study around the Barroso mine (Portugal): Baseline levels of lithium for assessing future exposure and risks from Li mining activity

The energetic green transition is increasing the demand for lithium (Li) exploitation. However, the Li supply faces challenges like limited reserves and environmental concerns. This pioneer study aims to characterize the Li concentrations in the region around the Barroso mine, in Portugal, by collecting and analyzing samples of cabbage, potato, drinking and irrigation water and soil from two nearby sites, and performing a preliminary exposure and risk assessment of local populations. Li levels ranged between 20 and 589 μg/kg in cabbages (n = 23), 2.3–21 μg/kg in potatoes (n = 21), 1.1–5.9 μg/L in drinking water (n = 10), 1.1–15 μg/L in irrigation water (n = 23) and 35–121 mg/kg in soils (n = 23). Significant differences in Li content between sampling sites were observed only for cabbage samples. The risk assessment revealed that none of the participants exceeded the provisional reference dose (p-RfD) (2 μg/kg bw/day), with a hazard quotient (HQ) < 1, suggesting no health concerns for the population. It is expected that the studied area will be affected by the future expansion of the mine concession, thus this pioneer study is crucial for future research as it establishes a initial database for evaluating the potential impact of mining activity on the environment and the population's exposure to Li.

Geochemical characteristics, Li source and genesis mechanism of thermal mineral water in Sichuan Basin, SW China

Thermal mineral water (temperature >25 °C) is a valuable resource, especially when it contains a certain amount of Li. In this study, an attempt was made to elucidate the factors affecting spatial distribution of lithium (Li) resources and interpret the formation mechanisms of thermal mineral waters in the Sichuan Basin. The spatial distribution, reservoir temperatures, and hydrochemical characteristics of thermal mineral waters were systematically analyzed in the Sichuan Basin, preliminarily revealing Li sources through hydrochemical methods. Results are showed as follows: (1) The Li-bearing (Li ≥ 1 mg/L) thermal mineral waters are mainly distributed in the southwestern part of the Sichuan Basin. There are three sites of thermal mineral waters with Li content greater than 25 mg/L with the hydrochemical type of Cl–Na type: Pengji Well (37.7 mg/L), Foguanghu Well (99.5 mg/L) and Zhougongshan New Well (118.0 mg/L). Among them, the Foguanghu Geothermal Well and the Zhougongshan New Well have high Li content and low Mg/Li (10.7 and 2.5), indicating great potential for utilization. (2) The Li-bearing thermal mineral waters are mainly formed in the fissure and pore reservoirs of the Middle–Lower Triassic. They are mainly affected by the dissolution of halite minerals and the deeply buried ancient seawater of the Triassic. The Li-bearing thermal mineral waters possess high contents of total dissolve solids (TDS) (4.3–230.0 g/L), Cl (0.7–142.9 g/L), Na (0.5–76.7 g/L), K (0.1–52.0 g/L), B (4.1–739.6 mg/L), and Li (1.5–118.0 mg/L). Moreover, the temperature of the geothermal reservoir ranges from 40 to 150 °C. The geothermal reservoir temperatures calculated by K–Mg and Mg–Li geothermometers are positively correlated with the Li content. (3) The Li source of the thermal mineral waters of the Sichuan Basin are dominated by multiple factors: first, Li concentration by evaporation, concentration and deep-seated metamorphism of ancient Triassic seawater; second, water–rock interaction between deep thermal mineral waters and mung bean rock or Emeishan basalt; and third, active tectonic activity and deep faulting induced upward flow of Li in deep fluids. This research enhances understanding of the formation of thermal mineral waters in the Sichuan Basin, offering scientific basis for the exploitation of Li resource.

Genesis of the Jiada pegmatite lithium deposit in the Ke’eryin ore field, western Sichuan, China: Evidence from whole-rock trace element and Li isotope

The origin and petrogenesis of pegmatite-type lithium deposits within the Songpan-Garze Fold Belt (SGFB) of western China remain subjects of debate. To provide further insight on this subject, this study investigated the whole-rock trace elements and whole-rock Li isotopic compositions of the two-mica monzogranite (TMG) from the Ke’eryin composite pluton, the Jiada albite pegmatite (AP) and albite-spodumene pegmatite (ASP) and their metasedimentary wall rocks within the Ke’eryin ore field in the eastern SGFB. Modeling of muscovite-dehydration melting based on the whole-rock trace elements (e.g., Li, Rb, and Sr) and Rayleigh dehydration modeling related to the whole-rock Li isotopes suggest that the Jiada pegmatites are unlikely to have originated from the low-degree partial melting of metasandstone (MS) of the Zhuwo Formation. Variations in the whole-rock trace elements and Li isotope between the TMG and the Jiada pegmatites are consistent with the evolution trend of magmatic fractionation. However, the whole-rock Li isotopic compositions of the AP and ASP display inverse variation characteristics with the muscovite Li isotopic compositions, with the AP exhibiting lower Li concentrations and higher whole-rock δ7Li values than ASP. Furthermore, the variation patterns of whole-rock trace elements do not align perfectly with the Rayleigh-type fractional crystallization processes, implying other geological processes would be also involved in the formation of the Jiada pegmatites. Collectively considering the Li isotope behavior during various geological processes, the observed variations in whole-rock Li isotopic compositions between AP and ASP can be explained by aqueous fluid enrichment during the pegmatitic melt evolution. This suggests that fractional crystallization and fluid exsolution jointly contributed to pegmatite formation and Li mineralization in the Jiada deposit. Moreover, the whole-rock δ7Li values of the wall rock of ASP (MS2) are lower than those of MS and the wall rock of ASP (MS1), primarily due to metasomatism by 6Li-enriched fluids expelled from ASP and the kinetic diffusion of Li isotopes. The high concentrations of highly mobile elements, especially Li and Cs, combined with the low whole-rock δ7Li value of the metasandstone, could serve as effective tracers for locating concealed orebodies and evaluating the metallogenic potential of Li mineralization.

Continental crust recycling in collisional zones: insights from Li isotope compositions of the syn-exhumation and post-collisional mafic magmatic rocks

Syn-exhumation and post-collisional mafic magmatism in continental collision orogenic belts may provide insights into the nature of orogenic lithospheric mantle and recycled continental components in continental subduction zones. Lithium and its isotopes have emerged as potentially valuable tools for shedding light on the origin of these magmas, given the contrast Li contents and isotopic compositions between the subducting continental crust and the mantle. Here, we present high-precision Li isotopes data for representative orthogneiss, continental eclogite, syn-exhumation and post-collisional mafic magmatic rocks from the North Qaidam orogen. The syn-exhumation mafic magmatic rocks have relatively higher Li contents (26.5–50.0 ppm) and lower δ7Li values (−1.01‰–1.48‰) than those of the post-collisional mafic magmatic rocks (Li = 11.1–22.7 ppm, δ7Li = 1.20‰–3.38‰), which are comparable to those of orthogneiss and continental eclogite, respectively. Dehydration and melting modelling results show that these mafic magmatic rocks have similar Li contents and δ7Li values to the continental eclogite- and orthogneiss-derived melts but are different from their derived fluids. Monte Carlo simulation for Li-Nd isotopes suggests the syn-exhumation and post-collisional mafic rocks could be derived from an enriched mantle source that contains ∼3–8% continental crustal components dominated by the orthogneiss and continental eclogite. The calculated results are consistent with the results from the previous study simulated by trace elements. Therefore, our results highlight Li isotopes as a potential tool to trace the nature of the continental crustal components recycling in continental subduction zones.

Redox Mechanisms upon the Lithiation of Wadsley-Roth Phases.

The Wadsley-Roth family of transition metal oxide phases are a promising class of anode materials for Li-ion batteries due to their open crystal structures and their ability to intercalate Li at high rates. Unfortunately, most early transition metal oxides that adopt a Wadsley-Roth crystal structure intercalate Li at voltages that are too high for most battery applications. First-principles electronic structure calculations are performed to elucidate redox mechanisms in Wadsley-Roth phases with the aim of determining how they depend on crystal structure. A comparative study of two very distinct polymorphs of Nb2O5 reveal two redox mechanisms: (i) an atom-centered redox mechanism at early stages of Li intercalation and (ii) a redox mechanism at intermediate to high Li concentrations involving the bonding orbitals of metal-metal dimers formed by edge-sharing Nb cations. Our study motivates several design principles to guide the development of new Wadsley-Roth phases with superior electrochemical properties.

Crystal chemistry and ionic conductivity of garnet-type solid-state electrolyte, Li5-xLa3(NbTa)O12-y

Crystal structures, microtopography, morphologies, elemental compositions, and ionic conductivity have been investigated for Li5-xLa3(Nb,Ta)O12-y using X-ray diffraction (XRD), field-emission analytical scanning and transmission electron microscopies (S/TEM), and electrochemical impedance spectroscopy. Using Rietveld refinements with powder XRD patterns, we determined that the number of Li atoms in the formula is less than 5 and that Li5-xLa3(NbTa)O12-y crystallizes in the cubic garnet structure with a space group Ia-3d. Sintering at varying temperatures (750–1000 °C) for 5 h in an ambient atmosphere produced distinct outcomes. Rietveld refinements disclosed that the sample sintered at 1000 °C (Li3.43(2)La3Nb1.07(2)Ta0.93(2)O12-y, a = 12.8361(7) Å, V = 2114.96(3) Å3) exhibited the highest ionic conductivity, while the 850 °C sample had the lowest conductivity, characterized by lower Li concentration and impurity phases (Li(Nb,Ta)3O88, Li2CO3). Analyses, including XRD and electron microscopy, confirmed the 1000 °C sample as a relatively phase pure with enhanced Li content (Li/La = 1.2), larger grains (15 μm), and uniform crystallinity. The 1000 °C sample introduced additional partially filled Li3 (96h) sites, promoting Li migration, and enhancing ionic conductivity. The resulting XRD pattern at 1000 °C has been submitted to the Powder Diffraction File as a reference.

Charge Carrier Dynamics of the Mixed Conducting Interphase in All‐Solid‐State Batteries: Lithiated Li1.3Al0.3Ti1.7(PO4)3 as a Case Study

AbstractAll‐solid‐state batteries relying on Li metal as negative electrode material and a ceramic electrolyte may severely suffer from unwanted interfacial processes. Here, Li1.3Al0.3Ti1.7(PO4)3 (LATP) serve as a model electrolyte which is known to form an ionic‐electronic, that is, mixed conducting interphase (MCI) when in contact with metallic Li or any other Li source. Li1.3+xAl0.3Ti1.7(PO4)3 with x = 0.2, 0.6 and 1.3 is prepared via ex situ chemical lithiation to mimic the formation of MCIs taking place otherwise operando. The preparation of large amounts of lithiated LATP with controlled Li contents allowed us to use nuclear and electric techniques to study local structures and ionic/electronic dynamics in detail. The results point to the formation of a core‐shell two‐phase morphology with the Li‐rich Li3Al0.3Ti1.7(PO4)3 phase covering the nonlithiated Li‐poor regions. The originally poor electronic conductivity σeon of 6.5 × 10−12 S cm−1 (293 K) increases by ≈3 orders of magnitude, hence reaching the order of 6.6 × 10−9 S cm−1 for x = 0.6. At even higher loadings (x = 1.3), a decrease in conductivity is seen, i.e., not exceeding alarming values for σeon. Quantifying electronic and ionic transport processes will help assessing the extent of damage through MCI formation and discussing whether any strategies to mitigate such formation is necessary at all.

Lithium Pollution and Its Associated Health Risks in the Largest Lithium Extraction Industrial Area in China.

Lithium (Li) is an important resource that drives sustainable mobility and renewable energy. Its demand is projected to continue to increase in the coming decades. However, the risk of Li pollution has also emerged as a global concern. Here, we investigated the pollution characteristics, sources, exposure levels, and associated health risks of Li in the Jinjiang River basin, the largest area for Li2CO3 production in China. Our results revealed the dominant role of Li extraction activities in the pollution of the river, with over 95% of dissolved Li in downstream river water being emitted from this source. Moreover, the Li concentration in aquatic plants (i.e., water hyacinth) and animals (i.e., fish) significantly increased from upstream to downstream areas, indicating a significant risk to local aquatic ecosystems. More importantly, our study found that local residents were suffering potential chronic noncarcinogenic health risks primarily from consuming contaminated water and vegetables. We also investigated the pollution characteristics of associated elements present in Li ores (e.g., Rb, Cs, Ni, and F-). By uncovering the remarkable impact of Li extraction activities on the Li content in ecosystems for the first time, our study emphasizes the importance of evaluating Li pollution from Li-related industrial activities, including mining, extraction, and recovery.

Developing Zn-2Cu-xLi (x < 0.1 wt %) alloys with suitable mechanical properties, degradation behaviors and cytocompatibility for vascular stents

Biodegradable Zn alloys show great potential for vascular stents due to their moderate degradation rates and acceptable biocompatibility. However, the poor mechanical properties limit their applications. In this study, low alloyed Zn-2Cu-xLi (x = 0.004, 0.01, 0.07 wt %) alloys with favorable mechanical properties were developed. The microstructure consists of fine equiaxed η-Zn grains, micron, submicron-sized and coherent nano ε-CuZn4 phases. The introduced Li exists as a solute in the η-Zn matrix and ε-CuZn4 phase, and results in the increase of ε-CuZn4 volume fraction, the refinement of grains and more uniform distribution of grain sizes. As Li content increases, the strength of alloys is dramatically improved by grain boundary strengthening, precipitate strengthening of ε-CuZn4 and solid solution strengthening of Li. Zn-2Cu-0.07Li alloy has the optimal mechanical properties with a tensile yield strength of 321.8 MPa, ultimate tensile strength of 362.3 MPa and fracture elongation of 28.0 %, exceeding the benchmark of stents. It also has favorable mechanical property stability, weak tension compression yield asymmetry and strain rate sensitivity. It exhibits uniform degradation and a little improved degradation rate of 89.5 μm∙year−1, due to the improved electrochemical activity by increased ε-CuZn4 volume fraction, and generates Li2CO3 and LiOH. It shows favorable cytocompatibility without adverse influence on endothelial cell viability by trace Li+. The fabricated microtubes show favorable mechanical properties, and stents exhibit an average radial strength of 118 kPa. The present study indicates that Zn-2Cu-0.07Li alloy is a potential and promising candidate for vascular stent applications. Statement of significanceZn alloys are promising candidates for biodegradable vascular stents. However, improving their mechanical properties is challenging. Combining the advantages of Cu and trace Li, Zn-2Cu-xLi (x < 0.1 wt %) alloys were developed for stents. As Li increases, the strength of alloys is dramatically improved by refined grains, increased volume fraction of ε-CuZn4 and solid solution of Li. Zn-2Cu-0.07Li alloy exhibits a TYS exceeding 320 MPa, UTS exceeding 360 MPa and fracture EL of nearly 30 %. It shows favorable mechanical stability, degradation behaviors and cytocompatibility. The alloy was fabricated into microtubes and stents for mechanical property tests to verify application feasibility for the first time. This indicates that Zn-2Cu-0.07Li alloy has great potential for vascular stent applications.