Increasing Lithium Content Research Articles

Investigation on Lithiated Half‐Heusler Alloy CoMnSi for Lithium‐Ion Batteries

ABSTRACTIn this work, we report on CoMnSi half‐Heusler alloy as a cathode material for secondary lithium‐ion batteries using ab initio methodology based on the density functional theory. The first‐principle calculations have been performed via the Wien2k package, which utilizes the full potential linearized augmented plane wave (FP‐LAPW) method to estimate the stability of the proposed structures and electronic characteristics while considering the exchange and correlation effects within the generalized gradient approximation. This alloy is found structurally stable with better electronic properties and with the alloying of lithium (Li) into the host lattice of CoMnSi, the metallic character is attained for LixCo1−xMnSi (0.125 ≤ x ≤ 1). We propose possible reactions at electrodes during the electrochemical lithiation. The addition of Li in place of the Co atom is found to be an endothermic process. With the increase in lithium concentration, a substantial change in the total and atom projected density of states around the Fermi level is observed. The theoretical maximum specific capacity (CM) and theoretical open circuit voltage (OCV) increase with the increase of lithium concentration in CoMnSi. The CM and OCV values attain a maximum value of around 297 mAh/g and 2.4 Volts for x ≥ 0.75, which means towards the complete conversion of CoMnSi into LiMnSi. The LiMnSi exhibits a similar structure as CoMnSi, which is also advantageous for the overall performance of lithium‐ion batteries to avoid any volumetric change during the charging and discharging cycles. Hence, the proposed half‐Heusler alloys have great potential to be used as a cathode material for lithium‐ion batteries.

Optimization of Tokamak Blanket Design to Minimize Neutron Flux on Magnets

Fusion energy, a promising solution to global energy challenges, replicates the same processes that give our sun its energy, notably through deuterium-tritium (D-T) fusion reactions that produce significant energy. This study explores the mechanics and challenges of various fusion reactions, emphasizing the pivotal role of lithium breeder blankets in producing tritium, essential for sustaining D-T fusion in tokamak reactors. The helium-cooled lithium lead (LiPb) blanket design was simulated to optimize tritium breeding and neutron flux management. Results indicated a tritium breeding ratio (TBR) of 1.15, surpassing the self-sufficiency target of 1.1, with further improvements through increased lithium content and blanket thickness. Effective neutron shielding ensured safe operational limits for reactor components. These findings demonstrate the feasibility of achieving self-sustaining fusion reactions, essential for the viability of fusion power as a sustainable energy source. Future research will focus on advanced materials, refined simulations, and enhanced cooling technologies to further optimize fusion reactor designs.

In-Situ Raman Spectroscopy of Li+ and Na+ Storage in Anodic Nanotubes

Anodizing is a high-voltage electrochemical conversion process that forms barrier-type oxide layers or self-organized nanoporous/nanotubular structures. So far, the Al2O3-like nanopores and TiO2-like nanotubes could be successfully synthesized on many valve metals and alloys.Recently, it become possible to form nanotubular structures on iron and consequently control the ratio of hematite (Fe2O3) to magnetite (Fe3O4) by subsequent thermal treatment.1 Electrochemically active nanotubes, such as self-organized TiO2 are of high interest in the battery field due to a unique one-dimensional (1D) geometry offering high volume expansion tolerance and applications without binders and conductive additives. Herein, we report an in - situ Raman spectroscopy study under current control for a better fundamental understanding of Li+/Na+ storage in nanotubes and correlate the structural fingerprints with the electrochemical data on differential capacity plots of d(Q–Q 0) dE –1.2 Real-time measurements revealed that the nanotubes had undergone two major phase transformations with increasing lithium content, disclosing the sequential steps of a lithium intercalation type of storage. In contrast, sodium-ion insertion induced no significant crystal structure modification but instead a slight crystallinity rupture, signifying a dominant nondiffusion-limited capacitive type of storage. The insight into the charge storage in a 1D material in relation to other nanostructures such as nanoparticles3 will be discussed.1. L. Fadillah, D. Kowalski, M. Vincent, C. Zhu, S. Kitano, Y. Aoki and H. Habazaki, ACS Applied Materials & Interfaces , 2023, 15, 52563-52570.2. M. Vincent and D. Kowalski, ACS Applied Nano Materials , 2023, 6, 6528-6537.3. M. Vincent, S. S. Kumar and D. Kowalski, Electrochimica Acta , 2023, 469, 143161. Figure 1

From consumption to excretion: Lithium concentrations in honey bees (Apis mellifera) after lithium chloride application and time-dependent effects on Varroa destructor.

Owing to its systemic mode-of-action and ease of application, lithium chloride (LiCl) is an ideal varroacide for the control of Varroa destructor infestations in honey bee colonies. To better understand how LiCl functions within a colony, we screened different parts of honey bee anatomy for lithium accumulation. We wanted to elucidate the time-dependent effects of LiCl on V. destructor and its metabolism within honey bees when they were fed continuous LiCl treatments, as well as evaluate potential adverse effects such as accumulation in the hypopharyngeal glands of nurse bees, which could negatively impact queens and larvae. Cage experiments reveal rapid acaricidal onset, with >95% mite mortality within 48 h of treatment. Bee hemolymph analysis supports these observations, showing a rapid increase in lithium concentration within 12 h of treatment, followed by stabilization at a constant level. Lithium accumulates in the rectum of caged bees (≤475.5 mg kg-1 after 7 days of feeding 50 mm LiCl), reflecting the bees' metabolic and excretion process. Despite concerns about potential accumulation in hypopharyngeal glands, low lithium levels of only 0.52 mg kg-1 suggest minimal risk to the queen and 1st- and 2nd-instar larvae. Cessation of LiCl treatment results in a rapid decline in mite mortality in the first 5 days, which increases again thereafter, resulting in mite mortality of 77-90% after 10 days. These findings help optimize LiCl application in colonies to achieve high Varroa mortality without unwanted adverse effects and provide important baseline data for future registration. © 2024 The Author(s). Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Structural, magnetic and magnetocaloric properties of Li-substituted La0.8K0.2-xLixMnO3 perovskite manganites

In this study we report the effect of lithium substitution on the structural, magnetic and magnetocaloric properties of La0.8K0.2-xLixMnO3 (0 ≤ x ≤ 0.075) samples synthesized by the sol–gel technique at low temperature. The investigated compounds crystallize in a rhombohedral system with R3¯c space group. The thermal variation of the magnetization under an applied magnetic field of 0.05 T showed that all our compounds exhibited a paramagnetic to ferromagnetic transition with decreasing temperature. With increasing lithium content, the Curie temperature TC, decreases from 287.4 K for x = 0 to 172.6 K for x = 0.075. The maximum of the magnetic entropy change, -ΔSMMax, is found to be 3.19, 3.51, 2.39 and 2.24 J kg−1 K−1 in a magnetic field change of 5 T for x = 0, 0.025, 0.05 and 0.075 respectively. The La0.8K0.175Li0.025MnO3 sample displays a higher maximum relative cooling power value of 320.5 J kg−1, equal to 78 % of that of gadolinium. Technically, this large value associated to a TC of 270 K makes the present sample very promising for magnetic refrigeration technology below room temperature.

Practical Evaluation of Anionic Redox in Li‐rich Cathode: An Electrochemical Study

AbstractLithium‐rich (Li‐rich) manganese‐based layered oxide materials are promising candidates for positive electrode materials due to their high energy density. However, challenges such as transition metal cation migration and irreversible anionic redox hinder their application. This study employs various electrochemical methods to systematically investigate three types of cathode materials: LiNi0.6Mn0.2Co0.2O2 (NCM622), Li1.12Ni0.39Mn0.49O2 (Li1.12), and Li1.2Ni0.2Mn0.6O2 (Li1.2). The findings indicate that an increase in lithium content leads to higher participation of anions in Anion Redox Reactions (ARRs), resulting in an augmented capacity. However, this also brings about significant polarization. The activation process of Li‐rich materials triggers the ARRs mechanism, resulting in a sharp increase in resistance. Voltage drops during shelving and cycling are closely tied to the ARRs occurring at high potentials in Li‐rich materials. To make the best use of the additional capacity associated with ARRs, it is essential to adjust the formation/cycling voltage in accordance with the characteristics of positive electrode materials with varying lithium contents. This study offers valuable insights for the design and utilization of Li‐rich materials.

First principles study of Be-doped graphdiyne as anode material for lithium-ion batteries

The performances of beryllium-doped graphdiyne (GDY), which is used as an anode material for lithium-ion batteries at various doping sites, are investigated by first-principles methods based on density functional theory. Calculations of the formation energy and cohesive energy of GDY at different doping concentrations indicate that beryllium-doped GDY has excellent prospects for experimental synthesis. More importantly, the beryllium-doped GDY exhibits good electrical conductivity. The adsorption energy for a single lithium atom on beryllium-doped GDY is –4.22 eV, which is significantly higher than that for boron, nitrogen-doped GDY, and intrinsic GDY. As the number of stored lithium atoms increases, the adsorption energy remains greater than the cohesive energy of solid lithium, and the average open-circuit voltage stays between 0 and 1 V, ensuring the safety of the battery. Additionally, the lithium storage capacity is increased to 881 mAh/g, which is 1.14 times that of undoped GDY and 2.36 times that of graphite. Meanwhile, the diffusion performance of lithium on beryllium-doped GDY is also enhanced. For the C<sub>III</sub> site doping system, by studying the ion transports at low, medium, and high lithium concentrations, we find that as the lithium concentration increases, the diffusion barriers are 0.38, 0.44, and 0.77 eV, respectively, making lithium ion movement more difficult, but still superior to those of other element-doped GDY. In summary, beryllium-doped GDY has great potential as an excellent anode material for lithium-ion batteries.

Comparative study of the reductive decomposition reaction of ethylene carbonate in lithium battery electrolyte: a ReaxFF molecular dynamics study.

Electrolyte decomposition and subsequent solid electrolyte interphase (SEI) are considered to be the primary cause of degradation of lithium batteries. We investigate the multiple factors that can affect the reductive decomposition pathways of ethylene carbonate (EC) and SEI formation using reactive molecular dynamics. Our simulations reveal the effects of lithium concentration, simulation temperature, and the imposition of external electric field on the decomposition reaction and pathways, respectively. The comparative results reveal the increasing lithium concentration has a strong influence on EC decomposition and its pathway at each temperature. Also, the increasing temperature and imposition of an external electric field have been found to non-electrochemically and electrochemically modify the decomposition pathways of EC. This study provides insights into not only the SEI chemistry in Li-ion batteries but also that in lithium metal batteries, which can potentially contribute to the design and optimisation of future novel battery materials and electrolyte solutions.

Detrimental Effects of Lithium on in vitro Seedlings of Pea (Vigna radiata)

The global demand for lithium-ion batteries has raised concerns about environmental consequences stemming from lithium leaching. In this study, we investigated the effects of lithium, sourced from Li2SO4, on in vitro seed germination and seedling growth of green moong (Vigna radiata). Our experiments used woody plant medium supplemented with 1 mg/l naphthalene acetic acid (NAA) and 2 mg/l benzyl adenine (BA). We observed that in vitro seed germination remained unaffected by lithium concentration. However, at concentrations of 3-5 mg/l of lithium, significant changes were observed in stem parameters including growth reduction, shoot tip damage and stem discolouration. Root growth was inhibited at lithium concentrations of 4 and 5 mg/l. Additionally, we noted leaf abscission, dark colouration and reduced leaf area in a dose-dependent manner. Necrotic lesions were not observed in the seedlings. Chlorophyll accumulation, phenolic content and peroxidase (POD) activity showed enhancement with increasing lithium concentration. Our data analysis strongly suggests dose-dependent toxicity in young seedlings under in vitro conditions. These findings shed light on the potential ecological implications of lithium leaching from retired batteries.

Evolution of Structures and Optical Properties in a Series of Infrared Nonlinear Optical Crystals LixAg1-xInSe2 (0 ≤ x ≤ 1).

In this work, a number of new infrared nonlinear optical (NLO) crystals of LixAg1-xInSe2, in which the ratio x of Li/Ag varies in a wide range from 0 to 1, are investigated. Structural analysis reveals that the space group of LixAg1-xInSe2 evolved from I4̅2d in AgInSe2 to Pna21 in LiInSe2 as x increases from low values (0, 0.2, 0.37) to large values (0.55, 0.78, 0.81, 1). Compared to other Li/Ag coexisting chalcogenides such as LixAg1-xGaS2 and LixAg1-xGaSe2, the structural distortions in LixAg1-xInSe2 are much more prominent. This may explain the limited crystallization region in the phase graph of the tetragonal structure LixAg1-xInSe2. The fundamental optical absorption edges in these LixAg1-xInSe2 compounds are determined from the direct electronic transitions and the band gaps Eg gradually increase as the lithium content increases, consistent with the first-principles calculations. The composition x = 0.78 is calculated to have a good set of optical properties with a large NLO coefficient (dpowder = 28.8 pm/V) and moderate birefringence (Δn ∼ 0.04). Accordingly, the Li0.78Ag0.22InSe2 crystal is grown by the modified Bridgman-Stockbarger method, and it exhibits a wide transparency range from 0.546 to 14.3 μm at the 2% transmittance level.

Density Functional Theory Study of Bilayer Borophene-Based Anode Material for Rechargeable Lithium Ion Batteries.

The bilayer borophene has been successfully fabricated in experiments recently and possesses superior antioxidation and robust metallic properties, which holds great promise for the future anode materials of Li-ion batteries. Herein, using first-principles calculations, two bilayer borophenes including P6/mmm or P6̅m2 symmetry groups with or without vacancy defects are comprehensively explored and acted as electrode materials with high performance in Li-ion batteries. The charge density difference, adsorption energies, and Bader charge analysis are calculated and discussed for single lithium adsorbed on bilayer borophene. The results shown that with the increase of lithium concentration, the adsorption energies are rapidly decreased due to the repulsion of boron atoms except for the P6̅m2 systems with double side adsorption and corresponding energies remain the narrow range. Meanwhile, the partial density of states shows metallic character after lithium adsorption and indicates good conductivity for the charge-discharge process. Furthermore, small diffusion barriers, low average open-circuit voltage, can be achieved, and large storage capacity is up to 930.2 mA h/g at the lower lithium content of 0.375. These results propose that bilayer borophene might be a good choice for anode material applications in future Li-ion batteries with fast ion diffusion and high power density.

High-Strength β-Phase Magnesium-Lithium Alloy Prepared by Multidirectional Rolling.

Magnesium-lithium alloys are popular in the lightweight application industry for their very low density. However, as the lithium content increases, the strength of the alloy is sacrificed. Improving the strength of β-phase Mg-Li alloys is urgently needed. The as-rolled Mg-16Li-4Zn-1Er alloy was multidirectionally rolled at various temperatures in comparison to conventional rolling. The results of the finite element simulations showed that multidirectional rolling, as opposed to conventional rolling, resulted in the alloy effectively absorbing the input stress, leading to reasonable management of stress distribution and metal flow. As a result, the alloy's mechanical qualities were improved. By modifying the dynamic recrystallization and dislocation movement, both high-temperature (200 °C) and low-temperature (-196 °C) rolling greatly increased the strength of the alloy. During the multidirectional rolling process at -196 °C, a large number of nanograins with a diameter of 56 nm were produced and a strength of 331 MPa was obtained.

Enhanced ionic conductivity of sulfide solid electrolyte with high lithium content based on cryomilling

Considering the high ion conductivity and good machining properties of lithium thiophosphate (LPS), it has attracted increasing attention as a solid electrolyte for all-solid-state batteries. Chemical and thermal stability can be significantly enhanced by increasing lithium content. However, in past reports, the lithium content of LPS is commonly less than 40 %. LPS with high lithium content (Li > 40 at%) shows low ion conductivity and high grain boundary resistance. In the present work, LPS with 47.2 at% lithium was prepared by cryomilling and solid-state reaction, avoiding crystallization and adhesion in the ball milling process. By improving the ball milling process, the ion conductivity (1.36 mS/cm) and ion activation energy (10.80 kJ/mol) were optimized by 106.1 % and 41.5 %, respectively. The resulting all-solid-state battery showed a high capacity retention of 104 % after 100 cycles.

An Improved Experiment for Measuring Lithium Concentration-Dependent Material Properties of Graphite Composite Electrodes.

The in situ curvature measurement of bilayer beam electrodes is widely used to measure the lithium concentration-dependent material properties of lithium-ion battery electrodes, and further understand the mechano-electrochemical coupling behaviors during electrochemical cycling. The application of this method relies on the basic assumption that lithium is uniformly distributed along the length and thickness of the curved active composite layer. However, when the electrode undergoes large bending deformation, the distribution of lithium concentration in the electrolyte and active composite layer challenges the reliability of the experimental measurements. In this paper, an improved experiment for simultaneously measuring the partial molar volume and the elastic modulus of the graphite composite electrode is proposed. The distance between the two electrodes in the optical electrochemical cell is designed and graphite composite electrodes with four different thickness ratios are measured. The quantitative experimental data indicate that the improved experiment can better satisfy the basic assumptions. The partial molar volume and the elastic modulus of the graphite composite electrode evolve nonlinearly with the increase of lithium concentration, which are related to the phase transition of graphite and also affected by the other components in the composite active layer. This improved experiment is valuable for the reliable characterization of the Li concentration-dependent material properties in commercial electrodes, and developing next-generation lithium batteries with more stable structures and longer lifetimes.

Temperature dependence of the EPR signal in ZnO

Ceramics based on zinc oxide doped with lithium was fabricated. It is shown that an increase in the lithium content in an amount up to 0.1% leads to a decrease in electrical conductivity, and then in the range up to 3% to its increase. The real and imaginary parts of the permittivity decrease with increasing lithium concentration over the entire range of measured frequencies (50 kHz - 3 MHz). Similarly, the signal of the EPR line with g-factor ~1.96 decreases. An analysis of the temperature dependence of the EPR signal intensity with a g factor of ~1.96 gives an activation energy of 0.06 eV, which practically coincides with the depth of shallow donors in ZnO. This makes it possible to identify the EPR signal with g-factor ~1.96 with oxygen vacancies.

The origin of gem spodumene in the Hamadan Pegmatite, Alvand Plutonic Complex, western Iran

ABSTRACTPegmatite bodies with a simple mineral composition are widespread within the Sanandaj-Sirjan Zone (SaSiZ), Zagros Orogen, Iran; however, gem-bearing pegmatite bodies are rare. There is a pegmatitic vein within the Hamadan garnet (± andalusite ± staurolite) schist adjacent to the Alvand Plutonic Complex (APC), south of Hamedan city (western Iran), in which large crystals of gem spodumene occur together with quartz, amazonite, beryl, tourmaline, and apatite. This spodumene-bearing pegmatite consists of four major zones with slightly different mineral compositions from the border to the core. The wall zone of quartz-rich granitoid and the intermediate zone of alkali granite have trondhjemitic compositions near the quartzolitic gem-bearing core zone. All parts of the vein are peraluminous in composition and exhibit S-type affinity. Two types of spodumene which have been distinguished in the core zone are colorless to very pale yellow and pink, transparent with vitreous luster and inclusion-free (eye clean) under 10× magnification. The different color in these minerals can be attributed to the slightly different chemical compositions, particularly lower Fe/Mn ratios in the pink material. The δ7Li values of the spodumene (+5.58 to +6.57‰) are indicative of the incorporation of middle continental crustal components in their genesis. Change in the mineral assemblage from tourmaline-bearing in the intermediate zone to spodumene + tourmaline in the core zone of the spodumene-bearing pegmatite is consistent with increasing lithium content from the wall zone to the core. Petrographic, geochemical, and isotopic data indicate that partial melting of middle-crustal Al-rich metapelitic source was followed by fractional crystallization to generate these rocks. In this concern, the required Li for the crystallization of spodumene was probably supplied by the breakdown of staurolite of the Hamadan schist and/or subsequent fractional crystallization of the parent magma. The results also demonstrate that the regional tectonic regime exerts a primary control on the occurrence and emplacement of the miarolitic pegmatite in the upper crust and the formation of gem spodumene during late-stage magmatic activities.

Lithium‐Ion Mobility in Layered Oxide Li2(La0.75Li0.25)(Ta1.5Ti0.5)O7 Containing Lithium on both Intra and Inter‐Stack Positions

AbstractWith the aid of neutron diffraction and electrochemical impedance spectroscopy, we have demonstrated the effect of the increase in lithium concentration and distribution on Li‐ion conductivity. This has been done through the synthesis of a layered oxide Li2(La0.75Li0.25)(Ta1.5Ti0.5)O7, with the so‐called Ruddlesden‐Popper type structure, where bilayer stacks of (Ta/Ti)O6 octahedra are separated by lithium ions, located in inter‐stack spaces. There are also intra‐stack spaces that are occupied by a mixture of La and Li, as confirmed by neutron diffraction. The distribution of lithium over both inter‐ and intra‐stack positions leads to the enhancement of Li‐ion conductivity in Li2(La0.75Li0.25)(Ta1.5Ti0.5)O7 compared to Li2La(TaTi)O7, which has a lower concentration of lithium ions, located only in inter‐stack spaces. The analyses of real and imaginary components of electrochemical impedance data confirm the enhanced mobility of ions in Li2(La0.75Li0.25)(Ta1.5Ti0.5)O7. While the Li‐ion conductivity needs further improvement for practical applications, the success of the strategy implemented in this work offers a useful methodology for the design of layered ionic conductors.

Multiscale Analysis and Safety Assessment of Fresh and Electrical Aged Lithium-Ion Pouch Cells Focusing on Mechanical Behavior

Analyzing the impact of electrical aging on the lithium-ion cell’s mechanical behavior and safety is an important factor to assess the crash safety of electric vehicles during their lifetime. In this study, fresh and electrical aged state-of-the-art NCM pouch cells were investigated. Aged cells, which were cycled electrically to 90% state of health, under laboratory conditions in electric vehicle battery modules were used. The used charging/discharging strategy represents real customer behavior based on accelerated driving profiles. First, it is shown that electrical aging has a significant influence on the anodes’ and separators’ mechanical properties, which had a lower mechanical strength and stiffness under tension. Additionally, quasi-static cylindrical indentation and three-point bending tests were performed to investigate aging effects on cell level at varying state of charge (SOC). Aged cells with 0% SOC showed a right-shifted force–displacement curve and a 29% lower maximum force compared to fresh cells. Fully charged, aged cells reached a similar maximum force to fresh cells, but faster temperature increase and higher temperature peaks after internal short circuit. Inductively coupled plasma optical emission spectrometry analyses confirmed an increased lithium content on the anode surface, which is indicated in literature as a reason for the increased exothermic reaction of the aged cells. The results indicate a higher safety risk for the aged investigated pouch cells under mechanical loads based on their changed mechanical properties and thermal runaway behavior.

Electrical Conductivity and Dielectric Relaxation in Ag1−xLixNbO3

The broadband electrical properties of Ag1−xLixNbO3 (ALNx) ceramics (x ≤ 0.1) together with AgNbO3 (AN) crystals were studied over a wide temperature interval of 20–800 K. For ALNx with x ≤ 0.05, a very diffused ferroelectric phase transition was observed. The position of the dielectric permittivity maximum in this phase transition is strongly frequency-dependent and is described well by the Vogel–Fulcher law. The freezing temperature decreases when the lithium concentration increases. Below the ferroelectric phase transition temperature, the dielectric dispersion is mainly caused by ferroelectric domain dynamics. Moreover, for ALN3 and ALN5 ceramics at very low temperatures (below 100 K), behavior typical of dipolar glasses is observed. At higher temperatures (above 650 K for ALN5), electrical conductivity effects become important. The DC conductivity increases with temperature according to the Arhenius law and the activation energy is highest in the antiferroelectric phase. Moreover, the activation energy is strongly dependent on the lithium concentration and it is greatest when x = 0.02.

Schottky barrier in Si-M structures of solid-state lithium-ion batteries

The results of measuring the charge-discharge characteristics of solid-state thin-film lithium-ion batteries with a nanocomposite anode based on the a-Si(Al) solid solution are presented. The charging characteristics of batteries have a feature in the form of a step on the gentle branch of the U(t) curve. It has been suggested and substantiated that the appearance of the step is related to the gradual compensation and change of the a-Si(Al) hole conductivity to electronic one as the lithium concentration increases. As a result, the a-Si(Al)|Ti ohmic contact becomes rectifying, and the electrons participating in the Faraday process have to overcome the Schottky barrier. The potential growth required to maintain the galvanostatic charge regime manifests itself as a step on the charge curve. Keywords: thin film solid-state lithium-ion battery, amorphous silicon, solid solution, sp3 hybridization, lithiation, Schottky barrier.