Lithium Source Research Articles

Direct production of lithium nitrate from the primary lithium salt by electrodialysis metathesis

As one of the most successful cathode materials, LiNi1-y-zMnyCozO2 (NMC) has become the preferred choice for automotive lithium-ion batteries (LIBs). Currently, its lithium source, LiOH, is not based on primary lithium salts and the route is unsustainable due to the large resource losses and high carbon footprint. In this study, a desirable alternative LiNO3 is synthesized directly from the primary lithium product LiCl and abundant NaNO3 by electrodialysis metathesis (EDM). Detailed online parameters (current/voltage/conductivity/pH/temperature) are recorded and product properties (volume/density/composition/purity) are also analyzed comprehensively. The effect of feed concentrations on the performance is intensively investigated as well. The results demonstrate that this one-step method with delicate ion metathesis can successfully prepare a highly pure (98.8%) and concentrated (118 g/L) LiNO3 solution. Meanwhile, the byproduct NaCl is virtually pure (>99%) and can also be used directly, so it is no burden to environment. Furthermore, a higher purity LiNO3 solid product (>99.7%) can be produced by integrating the evaporation process. The overall production cost has been carefully assessed and is as low as $0.219/kg. This work enables the volume production of LiNO3 in a green and cost-effective way, and broadens its application as a new precursor in the NMC synthesis, which can help to secure the supply chain of high-power LIBs.

Source and Enrichment Mechanism of Lithium in the Triassic Argillaceous Marine Sediments from Huangjinkou, Sichuan, China

AbstractIn the Triassic marine sediments, an obvious enrichment of lithium has been found. The source and enrichment mechanism of lithium is unknown. Here, we report trace and rare earth element and isotope analyses for Triassic sedimentary samples from core ZK601, recovered from the Huangjinkou anticline in the Xuanhan basin. Lithium concentrations from the Leikoupo and Jialingjiang formations are much higher than the average concentrations in the crust of eastern China and in other marine sediments. Lithium concentrations are highest at depths of 3300–3360 m (in argillaceous marine sediments), and Li is positively correlated with Rb, Ga, Zr, Nb and other trace elements. The range of δ7Li values in our samples is consistent with that in other Triassic marine carbonate rocks. Lithium concentrations and isotope ratios are negatively correlated in the argillaceous dolomite samples at depths of 3300–3360 m. We compared the results in this study with trace and rare earth elements in the clay from Sichuan and Chongqing, and propose that the clay in the argillaceous marine evaporites from Huangjinkou formed via the hydrolysis of volcanic ash during Early–Middle Triassic volcanic eruptions into brine basins, during which clay adsorbed Li from the brine and formed Li‐rich argillaceous dolomites. The addition and hydrolysis of volcanic ash in the evaporative brine is also related to the formation of a new type of polyhalite.

Lithium nitrate as a surplus lithium source for anode-free cell with Ni-rich (NMC811) cathode

Anode-free lithium metal batteries (AFLMBs) consisting of the copper current collector, carbonated-based electrolytes, and Ni-rich cathodes can be considered potential candidates for coming-generation energy storage devices. However, the capacity fade of Ni-rich (NMC811) cathode is very fast in carbonate electrolyte. It is essential to find way to increase the lithium inventory on the cathode side so that the issue of short cycle life associated with limited lithium can be addressed for AFLMBs. Here, we introduce lithium nitrate (LiNO3) as a cathode additive to modify the Ni-rich cathode. The additive is supposed to supply lithium inventory to compensate irreversible lithium loss and simultaneously result in the formation of stable solid electrolyte interphase (SEI) layers on the plated lithium surface. Interestingly in our AFLMBs configuration, we observe that the LiNO3 decomposes during the high voltage operation and strongly favors formation of a good solid-electrolyte interphase (LiF and Li3N) and cathodic-electrolyte interphase (CEI). The result also demonstrates that the cell with lithium nitrate additive exhibits much better Coulombic efficiency (CE) (97.69% after 30 cycles) compared to the cell with no additive (89.25% after 30 cycles). This work provides a new approach to extend the cycle life of anode-free lithium metal batteries.

Pre-Lithiation Strategies and Energy Density Theory of Lithium-Ion and Beyond Lithium-Ion Batteries

Pre-lithiation is the most effective method to overcome the initial capacity loss of high-capacity electrodes and has the potential to be used in beyond-conventional lithium-ion batteries. In this article we focus on two types of pre-lithiation: the first type can be applied to batteries in which the cathode has been fully lithiated but the anode has a large initial capacity loss, such as batteries made with lithium metal oxide cathode and silicon-carbon anode. The second type can be applied to batteries in which both electrodes are initially lithium-free and suffer a loss of lithium during the initial cycles, such as batteries made with sulfurized-polyacrylonitrile cathode and silicon-carbon anode. We describe the pre-lithiation procedures and electrode potential profiles during pre-lithiation corresponding to different pre-lithiation sources for both types of pre-lithiation. We also derive formulas for the theoretical specific energy and energy density that are based entirely on measurable parameters such as specific capacities, porosities, mass densities of two electrodes and extra lithium source, Coulombic efficiencies of electrodes, and the voltage of the cell. These formulas can be applied to different pre-lithiation sources to predict the specific energy of conventional and beyond-conventional lithium-ion batteries as a function of the type of pre-lithiation.

V2O3–Li3PO4 Composite: A New Type of Cathodic Active Material for Li‐Ion Batteries

AbstractA new type of cathodic active material for lithium‐ion batteries based on a composite of Li3PO4 and V2O3 is proposed in this work. Although the V2O3 component is almost inactive in the voltage range of 2–4.5 V versus Li+/Li, the mixture of the two components can deliver a larger reversible specific capacity of ≈190 mA h g−1 in the voltage range of 2–4.5 V at a current density of 15 mA g−1. X‐ray photoelectron spectroscopy data and cyclic voltammetry data suggest that the vanadium ions are probably oxidized and reduced repetitively upon cycling and that the V3+ ions are partially oxidized to V4+ and even V5+ ions during charging to 4.5 V. This distinctive lithium‐ion uptake and release phenomenon, in which Li3PO4 functions as a lithium source of surface conversion reaction, will introduce a new path for designing unique cathodic active materials for lithium‐ion batteries.

The auto-oxidative relithiation of spent cathode materials at low temperature environment for efficient and sustainable regeneration

The reasonable recycling of spent lithium ions batteries is urgently required and beneficial to new energy industry development to approach the "carbon neutral" target. It is urgent to understanding the structural evolution of spent lack lithium cathode materials during direct regeneration technology with low temperatures condition to avoid deficiencies of complex operation in existing technology. Herein, a novel approach was developed for direct regeneration of spent LiCoO2 materials with a successful structural repair and electrochemical performance recovery, which are composed of auto-oxidative process followed by pre-treatment process of dismantling, soaking and sintering. The auto-oxidative system was composed of LiBr as lithium source and dimethyl sulfoxide as solvent and oxygen donor. The recycled LiCoO2 material shows significantly close to capacity retention of 90.79% than that of the commercial LiCoO2 material. Based on the structural evolution mechanism analysis, the novel approach is still expected to be applied into regeneration of other spent cathode materials and guide an efficient and sustainable direction for the recycling of spent lithium ions batteries.

Direct Regeneration of Spent Lithium Iron Phosphate via a Low-Temperature Molten Salt Process Coupled with a Reductive Environment

A huge number of spent lithium-ion batteries (LIBs) have caused serious problems such as resource waste and environmental pollution. Lithium iron phosphate (LFP) is one of the major cathode materials in the spent LIBs. It is urgently needed to develop a safe, environmentally friendly, and cost competitive approach to regenerate the LFP cathode collected from the spent LIBs. The nitrate molten salt process has been utilized to regenerate layered cathode materials, which are nevertheless non-compatible with the LFP regeneration process. The LFP crystal lattice will be destroyed during the molten salt process by the oxidative environment, where Fe(II) is oxidized to Fe(III). A new approach is proposed in this work to tackle this issue, where a low-temperature molten salt process is coupled with a reductive environment to suppress oxidation of Fe(II). In detail, lithium nitrate is used as a molten salt medium and lithium source simultaneously. Sucrose is used as a carbon source to provide a reductive environment. Through a short molten-salt relithiation step at 300 °C and further annealing process at 650 °C, LFP particles with a lithium-deficient and damaged structure can be successfully recovered. The rapid lithium replenishment process exposes more (101) crystal planes facilitating lithium-ion transportation. As a result, the regenerated LFP delivers a specific capacity of 145 mAh g–1 at 0.5C, which is more than a 13% increase relative to the spent LFP and has a better rate performance than pristine LFP at 5C. In addition, we also point out that the LFP is converted to Li3PO4 with the increase in lithium source and the extension of treatment time. This work provides a new promising way to regenerate spent LFP cathodes.

Lithium-rich geothermal brines in Europe: An up-date about geochemical characteristics and implications for potential Li resources

Lithium (Li) is a strategic metal - especially for batteries in electric vehicles - for which worldwide demand is constantly increasing. Presently, several investigations are examining if a part of lithium could be extracted from deep European geothermal fluids. Among the data from geothermal and hydrocarbon wells found in the literature review carried out by BRGM and EIFER, only six areas stand out with deep fluids containing high Li concentrations from 125 to 480 mg/l in Italy, Germany, France and the United-Kingdom. Except the UK fluid, which has a relatively low salinity (TDS = 19 g/l) and reservoir temperature (around 52 °C), these deep Li-rich fluids are Na-Cl brines (TDS ≥ 56 g/l) with high concentrations of Na (> 18 g/l) and Cl (> 25 g/l) and high temperatures (≥ 120 °C and up to 380 °C in Italy). If high TDS and temperature values seem to be key factors for triggering high Li concentrations in such fluids, these two factors alone cannot be sufficient. Indeed, our study confirms that Li concentrations not only depend on temperature and fluid salinity, but also on the type of reservoir rock and its mineralogical constituents, as demonstrated by the good results obtained using two different Na-Li thermometric relationships existing in the literature. One fits well with the brines from low to high temperature (120–250 °C) reservoirs in deep tectonic sedimentary basins over a crystalline basement (France, Germany) and the other with the fluids from ultra-high temperature (≥ 300 °C) reservoirs in volcano-sedimentary environment (Italy). If the high chloride concentrations values in these brines mainly depend on the fluid origin (evaporated seawater or freshwater, halite dissolution, primary neutralization fluids or parent-geothermal fluids in high-temperature and -pressure volcanic environments, water mixing, etc.), the other aqueous major species are mostly controlled by hydrothermal water-rock interaction processes. At these temperatures (≥ 120 °C), the fluid-rock interaction processes are generally dominated by plagioclase and K-feldspar dissolution, followed by albitization of these minerals, dissolution of white micas and biotite, precipitation of illite, and chloritization. According to the two Na-Li thermometric relationships, existing mineralogical and isotopic data, this study suggests that the main sources of Li are white micas and biotite dissolution. Among the European areas, it shows that the Upper Rhine Graben (URG) along the French/German border is probably the most promising zone. For the URG geothermal brines, the main source and control of lithium, at about 225 °C, at reservoir depth, is probably the up to 450-m-thick micaceous continental sandstone of Triassic Buntsandstein. A minor contribution from the granite basement can also not be excluded. Though the Li concentration values of these brines (≥ 150 mg/l) seem to be favourable for geothermal Li exploitation, it is essential to make an as accurate as possible estimate of the Li resource of these brines, design the Li extraction process, and examine the economic conditions of its exploitation.

NaMn0.2Fe0.2Co0.2Ni0.2Ti0.2O2 high-entropy layered oxide – experimental and theoretical evidence of high electrochemical performance in sodium batteries

Li-ion batteries, widely used in portable electronics, electric vehicles, and energy storage systems, are an integral element of our daily life. However, the limitation of lithium sources, which leads to high prices, prompts the search for alternatives. Recently there has been noticed a rapid interest in Na-ion batteries technology. Especially, suitable cathode structures are investigated to accumulate larger sodium ions. In this paper, the high entropy layered oxide NaMn0.2Fe0.2Co0.2Ni0.2Ti0.2O2 is presented which achieves superior electrochemical properties with a stable capacity of ca. 180 mAh g−1. The understanding of its high performance is based on a complex study of the multiphase intercalation mechanism. The combination of advanced structural analysis by XAS, in situ XRD, TEM, and computational DFT modelling gives a new concept on the nature of O3-P3 structure reorganization. The presented experimental and theoretical evidence indicates that the P3 phase of layered oxides is energetically favourable for a lower sodium content for specific transition metal-oxide pair distance. Fundamental understanding of the nature of phase transformation is crucial for tailoring structural composition, where the desirable O3-P3 reorganization will occur, resulting in achieving high-performance cathodes.

High rate performance of Lithium-ion batteries with Co-free LiNiO2 cathode

Co-free LiNiO2 (H-LNO) nanoparticles were synthesized by the urea-based hydrothermal synthesis in the presence of sodium dodecyl sulfate as an anionic surfactant, followed by a high-temperature calcination process with a lithium source. Compared to the LiNiO2 samples prepared via the co-precipitation method (C-LNO), the H-LNO samples exhibited superior electrochemical properties, such as charge/discharge capacity, rate capability, and cycle performance. Electrochemical tests showed that the H-LNO cathode reached an ultra-high initial discharge capacity of 211.9 mAh/g at 0.1C and maintained a capacity of 131.9 mAh/g at 5C, approximately twice greater than that of the C-LNO cathode. The H-LNO sample retained 77.33 % of its capacity, which is higher than that for the C-LNO sample (65.84 %) after 50 cycles at 0.5C. These results were attributed to the combined effect of the high Li+ diffusion coefficient and low charge transfer resistance, suggesting that the H-LNO powder is beneficial for practical applications in Li-ion batteries.

In-situ self-assembly synthesis of low-cost, long-life, shape-controllable spherical Li4Ti5O12 anode material for Li-ion batteries

Li4Ti5O12 (LTO) is the most promising anode material for lithium-ion batteries owing to its excellent cycle stability and safety. However, the electrochemical performance of LTO at high rates is limited by its low conductivity. Generally, LTO preparation requires organic titanium sources, which are expensive. In this study, inexpensive H2TiO3 was used as the titanium source, LiOH‧H2O served as the lithium source, and NH3‧H2O was added to control the pH of the solution. Simple one-step liquid-phase deposition and calcination were performed for obtaining in situ self-assembled LTO submicron spheres with stable morphology and excellent electrochemical performance. According to electrochemical performance tests, the sample calcined with 4 mL of 25% NH3‧H2O at 700 °C (LTO-4–700) exhibited the best performance. Its discharge capacity remained at 176.4 mAh g−1 over 100 cycles at 87.5 mA g−1 and retained at 136.7 mAh g−1 over 500 cycles at 875 mA g−1, and its specific capacity was 105.6 mAh g−1 over 1000 cycles, even at a current of 1750 mA g−1 with a retention rate of 96.7%. Furthermore, LTO-4–700 exhibited excellent rate performance at 3500 mA g−1 compared to other samples. Cyclic voltammetry and electrochemical impedance spectroscopy confirmed that submicron spherical LTO-4–700 had a high Li+ migration rate and low electrochemical impedance.

Forward Osmosis to Concentrate Lithium from Brine: The Effect of Operating Conditions (pH and Temperature)

The development of battery technology is the driving force behind the increasing demand for lithium, which has resulted in a decreased supply of lithium in the market and continues to be a challenge for the industry. In response to these conditions, the development of lithium recovery technology continues, and there is a search for sources of lithium that are easier to recover. One source of lithium that has the potential to be processed is geothermal brine using forward osmosis technology. The aim of this study was to determine the best operating conditions for forward osmosis as a substitute for conventional evaporation methods. The parameters to be optimized included pH and operating temperature. The flow rate in the forward osmosis process was controlled by two litres per hour (LPH), while the concentration of the draw solution was 6M. The operating temperature variations used were 40

Lithium and magnesium separation from brines by hybrid capacitive deionization

Presented work deals with the problem of separating lithium and magnesium from brines. A similar size of ionic radius characterizes the Li+ and Mg2+; hence, separating these elements could be problematic. The hybrid capacitive deionization (HCDI) with lithium‑manganese‑titanium oxides was employed as a potential process for separating lithium and magnesium ions from aqueous solutions. During the investigation, the thermodynamics factors were determined. The enthalpy of activation, the entropy of activation and the Gibbs energy of activation for accumulation Li+ and Mg2+ by Eyring-Polanyi and energy activation by Arrhenius equations were calculated for explanation the separation phenomenon. Next, the HCDI for binary and multicomponent solutions were conducted. The critical role in achieving high βLi/Mg plays the activity coefficient of the initial feed, and the value of a voltage applied in constant voltage electric mode. With the increasing value of brines' activity coefficient, the separation factor βLi/Mg lift when the concentration of lithium ions decreases. HCDI with LMTO material adsorbed lithium ions with βLi/Mg at 2.14 and released Li+ with over 70% efficiency. The proposed HCDI process employed LMTO sorptive material could be considered a potential method for separating lithium and magnesium from lithium sources.

A Flower-Like Sb4O5Cl2 Cluster-based material as anode for potassium ion batteries

Potassium ion batteries (PIBs) have attracted tremendous attentions based on the fact that lithium ion batteries have been increasingly challenged by the uneven distribution and ultralow reserve of lithium sources. Safety concern has raised requirement for acceptable anode materials with high capacity and favorable working-potential. Here, a 3D flower-like antimony oxychloride (Sb4O5Cl2) that is synthesized via a mild hydrothermal method, is firstly employed as anode material for PIBs, where a high reversible capacity of 530 mAh g−1 could be achieved at current density of 50 mA g−1, with decent cycling performance and rate capability. Kinetic analyses based on electrochemical measurements evidence that the Sb4O5Cl2 electrode could deliver high K+ ion diffusion coefficient, and density functional theory calculations are also conducted to probe the migration paths of K+ ion in Sb4O5Cl2 and the electronic structure involved in the electrochemical kinetics behaviors. The K+ ion storage mechanism during potassiation/de-potassiation is investigated via ex-situ X-ray diffraction, high resolution transmission electron microscope and theoretical calculations, and a reversible process involving both conversion-type and alloy/de-alloy reactions is established.

Elastomeric electrolytes for high-energy solid-state lithium batteries.

The use of lithium metal anodes in solid-state batteries has emerged as one of the most promising technologies for replacing conventional lithium-ion batteries1,2. Solid-state electrolytes are a key enabling technology for the safe operation of lithium metal batteries as they suppress the uncontrolled growth of lithium dendrites. However, the mechanical properties and electrochemical performance of current solid-state electrolytes do not meet the requirements for practical applications of lithium metal batteries. Here we report a class of elastomeric solid-state electrolytes with a three-dimensional interconnected plastic crystal phase. The elastomeric electrolytes show a combination of mechanical robustness, high ionic conductivity, low interfacial resistance and high lithium-ion transference number. The in situ-formed elastomer electrolyte on copper foils accommodates volume changes for prolonged lithium plating and stripping processes with a Coulombic efficiency of 100.0percent. Moreover, the elastomer electrolytes enable stable operation of the full cells under constrained conditions of a limited lithium source, a thin electrolyte and a high-loading LiNi0.83Mn0.06Co0.11O2 cathode at a high voltage of 4.5volts at ambient temperature, delivering a high specific energy exceeding 410watt-hours per kilogram of electrodepluselectrolyte. The elastomeric electrolyte system presents a powerful strategy for enabling stable operation of high-energy, solid-state lithium batteries.

Spinel LiMn<sub>2</sub>O<sub>4</sub> Nanorods via Template–Engaged Method and as Cathode Materials for Li-Ion Batteries

Spinel LiMn2O4 nanorods were prepared by a hydrothermal method followed by solid-state lithiation. The produce β-MnO2 nanowire as template, and LiOH·H2O was used as lithium source. The spinel LiMn2O4 nanorods samples were characterized by SEM, XRD, (HR)TEM, and galvanostatic charge/discharge profile measurement. Compared with the LiMn2O4 nanoparticles, the LiMn2O4 nanorods showed superior cycling stability, better rate capability, good high temperature performance, and delivered a discharge capacity of 122 mAh/g (at 1 C, 100 cycles).

Prospects and priorities for the reconstruction and development of lithium mining production on the basis of domestic raw materials

The prospects of lithium as a component of new energy are considered. Provides data on the resources of lithium mineral raw materials. Variants of the reconstruction of lithium production facilities in Russia from domestic raw materials are evaluated in order to solve the problem of import substitution. Attention is focused on the choice of objects of priority industrial development and the need to create modern technologies for processing lithium raw materials. It is shown that the restored Zabaikalsk mining and processing plant can be a reliable source of lithium when using new technological solutions for extracting lithium and associated useful components from primary ores and waste of spodumene ores.

Active material and interphase structures governing performance in sodium and potassium ion batteries.

Development of energy storage systems is a topic of broad societal and economic relevance, and lithium ion batteries (LIBs) are currently the most advanced electrochemical energy storage systems. However, concerns on the scarcity of lithium sources and consequently the expected price increase have driven the development of alternative energy storage systems beyond LIBs. In the search for sustainable and cost-effective technologies, sodium ion batteries (SIBs) and potassium ion batteries (PIBs) have attracted considerable attention. Here, a comprehensive review of ongoing studies on electrode materials for SIBs and PIBs is provided in comparison to those for LIBs, which include layered oxides, polyanion compounds and Prussian blue analogues for positive electrode materials, and carbon-based and alloy materials for negative electrode materials. The importance of the crystal structure for electrode materials is discussed with an emphasis placed on intrinsic and dynamic structural properties and electrochemistry associated with alkali metal ions. The key challenges for electrode materials as well as the interface/interphase between the electrolyte and electrode materials, and the corresponding strategies are also examined. The discussion and insights presented in this review can serve as a guide regarding where future investigations of SIBs and PIBs will be directed.

Lithium ion sieve modified three-dimensional graphene electrode for selective extraction of lithium by capacitive deionization

Faced with the strong demand of clean energy, development of lithium source is becoming exceedingly vital. Spinel-type manganese oxide (λ-MnO2) is a typical lithium ion sieve material. Herein, the conductive three-dimensional (3D) lithium ion sieve electrode material was fabricated by in-situ growth of λ-MnO2 on 3D reduced graphene oxide (3D-rGO) matrix for Li extraction by capacitive deionization (CDI). The λ-MnO2 modified rGO (λ-MnO2/rGO) retained the 3D network structure with uniform distribution of λ-MnO2 nanosheets on rGO. Electrochemical characterization demonstrated its high conductivity and fast lithium ion diffusion rate. By adjusting the rGO concentration, λ-MnO2 activity was improved significantly. With λ-MnO2/rGO as a positive electrode (activated carbon as negative electrode), the corresponding CDI system was successfully applied for the selective extraction of Li+. The final rGO content in the λ-MnO2/rGO was attained by thermogravity analysis. With the appropriate rGO content (15.5%), the obtained λ-MnO2/rGO electrode achieved the optimal Li+ adsorption amount. The corresponding λ-MnO2/rGO-based CDI cell showed good selectivity and high cycle stability. When applied to the extraction of lithium from synthetic salt lake brine, the electrode also obtained high Li+ adsorption amount with good selectivity.

Exploring the Effects of Greek Yogurt Supplementation and Exercise Training on Serum Lithium and Its Relationship With Musculoskeletal Outcomes in Men.

Dairy products can act as a dietary source of lithium (Li), and a recent study in university-aged males demonstrated that Greek yogurt (GY) supplementation augmented gains in fat free mass, strength and bone formation after 12 weeks of resistance exercise training compared to carbohydrate (CHO) pudding supplementation. Here, we performed secondary analyses to explore whether GY would alter serum Li levels and whether changes in serum Li would associate with changes in body composition, strength, and bone turnover markers. Results show that the GY group maintained serum Li levels after exercise training, whereas the CHO group did not. Maintaining/elevating serum Li levels was also associated with greater gains in strength and reductions in bone resorption. However, controlling for other dietary factors in GY such as protein and calcium weakened these associations. Thus, future studies should assess the causative role, if any, of dietary Li alone on strength and bone resorption in humans.