Search Results (380)

Precise control over defect structures is essential for tuning the functional properties of lithium niobate (LiNbO₃) crystals. Although the threshold effect of Hf⁴⁺ doping is well recognized, its underlying atomic-scale mechanism, especially in systems co-doped with luminescent rare earth ions, remains unclear. In this study, we combine experimental and theoretical approaches to elucidate the Hf⁴⁺ concentration-driven threshold behavior in Dy: LiNbO₃ crystals. A series of crystals with Hf⁴⁺ concentrations of 2, 4, 6, and 8 mol% were grown using the Czochralski method. Characterization through XRD and IR spectroscopy identified a threshold near 4 mol%, evidenced by an inflection in lattice constants and a pronounced blue shift of the OH⁻ absorption peak. UV–Vis–NIR absorption spectra revealed a systematic enhancement of Dy³⁺f–f transition intensities, linking the global defect structure to the local crystal field of the optical activator. First-principles calculations showed that Hf⁴⁺ ions preferentially occupy Li sites, repairing antisite Nb defects ($\mathrm{N}{\mathrm{b}}_{\mathrm{Li}}^{4+}$) below the threshold, and incorporate into Nb sites beyond it, inducing structural reorganization. Electron Localization Function analysis visualized strengthened Hf-O covalent bonding in the post-threshold regime. This work establishes a complete atomic-scale picture connecting dopant site preference, chemical bonding, and macroscopic properties, providing a foundational framework for the rational design of advanced LiNbO₃-based materials. Full article

Silicon-graphite anodes offer a practical route to increase the energy density of lithium-ion batteries (LIBs), but their widespread adoption is hampered by cyclic instability due to huge volume changes of silicon during lithiation/delithiation process. Another fallout of LIBs capacity gain is growing safety concerns due to fire risks, associated with the uncontrolled release of chemical energy. Herein, we test a hexakis(fluoroethoxy)phosphazene (HFEPN) as a multifunctional electrolyte additive designed to mitigate both issues. The flammability of HFEPN-containing electrolytes was evaluated using a self-extinguishing time test, while the electrochemical performance was assessed in Si/C composite||NMC pouch cells under a progressively accelerated cycling protocol. It is shown that the additive fully imparts flame-retardant properties to the electrolyte at a 15 wt% loading. Despite forming a more stable solid–electrolyte interphase (SEI) with enhanced interfacial kinetics the additive did not improve the cycling stability of the Si/C-based cells. The cells with 15 wt% HFEPN retained 43% of capacity after 70 cycles, comparable to 46.5% for the reference electrolyte. The diffusion limitations imposed by the increased electrolyte viscosity are assumed to offset the interfacial benefits of the additive. Thus, alongside the improved synthetic route, this study demonstrates that while HFEPN functions as an effective flame retardant and SEI modifier, its practical benefits for silicon anodes are limited at high concentrations by detrimental effects on electrolyte transport properties and should be improved in future molecular design efforts. Full article

Lithium (Li) is a critical metal element in geothermal systems, yet its enrichment mechanism in coastal geothermal waters remains poorly understood. This study focuses on the Xiamen coastal geothermal system, located in the South China granitic reservoir at the front of the Pacific subduction zone. Self-organizing map (SOM) classification, hydrogeochemical analysis, hydrogen–oxygen isotopic constraints, and a three end-member mass balance model were applied to identify the sources and enrichment mechanisms of Li. The geothermal waters are classified into two types: inland low-TDS (Cluster-1) and coastal high-TDS (Cluster-2). Isotopic data indicate a mixture of meteoric water and seawater as the recharge source. The model shows that seawater and groundwater mixing accounts for 2–45% of Li concentration, with over 55% derived from the rock end-member. The leaching of 0.002–0.187 kg of granite per liter of geothermal water explains the observed Li levels. Elevated temperature and low pH enhance Li⁺ release from silicate minerals, and reverse cation exchange further amplifies this process. A strong positive correlation between the CAI-II index and Li⁺ concentration reveals a synergistic effect of ion exchange in high-salinity environments. Overall, the results provide a quantitative framework for understanding Li enrichment and evaluating resource potential in coastal geothermal systems. Full article

Improving electronic and ionic transport and the structural stability of electrode materials is essential for the development of advanced lithium-ion batteries. Despite its great potential as a high-power anode, Ti₂Nb₁₀O₂₉ (TNO) still underperforms due to its unsatisfactory electronic and ionic conductivity. Here, a TNO/carbon microtube (TNO@CMT) composite is constructed via an ethanol-assisted solvothermal process and controlled annealing. The hollow carbon framework derived from kapok fibers provides a lightweight conductive skeleton and abundant nucleation sites for uniform TNO growth. By tuning precursor concentration, the interfacial structure and loading are precisely regulated, optimizing electron/ion transport. The optimized TNO@CMT-2 exhibits uniformly dispersed TNO nanoparticles anchored on both inner and outer CMT surfaces, enabling rapid electron transfer, short Li⁺ diffusion paths, and high structural stability. Consequently, it delivers a reversible capacity of 314.9 mAh g⁻¹ at 0.5 C, retains 75.8% capacity after 1000 cycles at 10 C, and maintains 147.96 mAh g⁻¹ at 40 C. Furthermore, the Li⁺ diffusion coefficient of TNO/CMT-2 is 5.4 × 10⁻¹¹ cm² s⁻¹, which is nearly four times higher than that of pure TNO. This work presents a promising approach to designing multi-cation oxide/carbon heterostructures that synergistically enhance charge and ion transport, offering valuable insights for next-generation high-rate lithium-ion batteries. Full article

The growing demand for lithium-ion batteries (LIBs) is driving a rapid increase in the volume of spent cells which—as hazardous waste—must be managed effectively in accordance with circular-economy principles. Hydrometallurgical recycling allows the recovery of critical metals at far lower environmental cost than primary mining. This paper presents a method for obtaining metallic nickel from sulfate leach solutions produced by leaching the so-called “black mass” derived from shredded LIBs. Nickel electrodeposition was performed on a stainless-steel cathode with Ti/Ru-Ir anodes at 60 °C and pH 3.0–4.5. Two process variants were examined. Variant A—with a decreasing Ni²⁺ concentration (49 → 25 g L⁻¹)—achieved a current efficiency of 60–88%, but the deposits were non-uniform and prone to flaking. Variant B—in which the bath was stabilized by the continuous dissolution of Ni(OH)₂ (maintaining Ni²⁺ at 35–40 g L⁻¹) and amended with PEG-4000, H₃BO₃ and Na₂SO₄—reached higher efficiency (78–93%) and produced uniform, bright deposits up to 0.5 mm thick with a purity >90%. The results confirm that keeping the nickel concentration constant and appropriately modifying the electrolyte significantly improve both the qualitative and economic aspects of recovery, highlighting electrolysis as an efficient way to process LIB waste and close the nickel stream within the material cycle. Full article

The rise in thermal runaway events within electric vehicle (EV) battery systems requires anticipatory models to predict critical safety failures during operation. This investigation develops a multi-physics digital twin framework that links electrochemical, thermal, and structural domains to replicate the internal dynamics of lithium-ion packs in both normal and faulted modes. Coupled simulations distributed among MATLAB 2024a, Python 3.12-powered three-dimensional visualizers, and COMSOL 6.3-style multi-domain solvers supply refined spatial resolution of temperature, stress, and ion concentration profiles. While the digital twin architecture is designed to accommodate different battery chemistries and pack configurations, the numerical results reported in this study correspond specifically to a lithium NMC-based 4S3P cylindrical cell module. Quantitative benchmarks show that the digital twin identifies incipient thermal deviation with 97.4% classification accuracy (area under the curve, AUC = 0.98), anticipates failure onset within a temporal margin of ±6 s, and depicts spatial heat propagation through three-dimensional isothermal surface sweeps surpassing 120 °C. Mechanical models predict casing strain concentrations of 142 MPa, approaching polymer yield strength under stress load perturbations. A unified operator dashboard delivers diagnostic and prognostic feedback with feedback intervals under 1 s, state-of-health (SoH) variance quantified by a root-mean-square error of 0.027, and mission-critical alerts transmitting with a mean latency of 276.4 ms. Together, these results position digital twins as both diagnostic archives and predictive safety envelopes in the evolution of next-generation EV architectures. Full article

This study introduces a new theoretical framework for the ferroelectric phase transition in lithium niobate (LiNbO₃), which explicitly incorporates electrostatic interactions between both first and second nearest-neighbor ions. This extended model is applied to estimate the inverse quality factor (Q⁻¹), the equivalent mechanical resistance (R_m), and the Curie temperature (Tc) of pure and titanium-doped lithium niobate (LiNbO₃:Ti). The proposed analytical expression for Tc is given by: $T_C^{*}={\displaystyle \frac{2\sqrt{\frac{-p^{*}}{3}}\mathrm{c}\mathrm{o}\mathrm{s}\left(\frac{{\theta }^{*}}{3}\right)-\frac{B^{*}}{3}}{2\sqrt{\frac{-p}{3}}\mathrm{c}\mathrm{o}\mathrm{s}\left(\frac{\theta }{3}\right)-\frac{B}{3}}} T_C$. The analysis reveals that variations in Q⁻¹ and Tc are governed by factors such as ionic mass, charge, and defect structure. The theoretical predictions show good agreement with experimental data reported in the literature—particularly for Q⁻¹ in pure LiNbO₃ and for Tc in Ti-doped LiNbO₃—thus validating the reliability of the proposed model. Moreover, at constant temperature, both the inverse quality factor and the equivalent mechanical resistance decrease as the Ti concentration increases. This trend highlights that titanium doping enhances the acoustic performance of LiNbO₃ substrates, making them more suitable for high-performance surface acoustic wave (SAW) device applications. Full article

The continuous solid solution series based on the ion exchangeable Dion-Jacobson layered perovskites, A_1−xA′_xLaNb₂O₇ (A/A′ = Li, Na, K, Rb, Cs; 0 ≤ x ≤ 1), has been investigated to illuminate the relationship between composition and structure. Topochemical synthesis of the solid solutions from combinations of various alkali metal cations has been achieved by reacting pure end members (ALaNb₂O₇) at appropriate ratios and temperatures. All adjacent sets of alkali metals (Li/Na, Na/K, K/Rb, and Rb/Cs) readily formed solid solutions, while only the one non-adjacent solid solution, K_1−xCs_xLaNb₂O₇ (K/Cs), could be obtained. Local cation coordination and the corresponding layer alignments vary as a function of composition where the relative concentration of the larger cation dictates structure. Thermal analysis of the solid solutions, A_1−xA′_xLaNb₂O₇ (A/A′ = Li, Na, K) showed that the lithium- and sodium-containing compositions were thermally unstable. This study demonstrates that the systematic variation in average cation sizes in the solid solution series allows for structural control in these important perovskite hosts. Full article

Hydrometallurgy is currently the mainstream industrial process for recovering valuable components (nickel, cobalt, manganese, lithium, etc.) from spent ternary lithium-ion battery cathode materials. During the crushing of lithium batteries, cathode materials, anode materials (graphite), and electrolytes become mixed. Consequently, fluoride ions inevitably enter the leaching solution during the hydrometallurgical recycling process, with concentrations as high as 100–300 mg/L. These fluoride ions not only adversely affect the quality of the recovered precursor products but also pose environmental risks. To address this issue, this study employs a synthesized lanthanum–zirconium (La@Zr) composite material, with a specific surface area of 67.41 m²/g and a pore size of 2–50 nm, which can reduce the fluoride ion concentration in the leaching solution to below 5 mg/L, significantly lower than the 20 mg/L or higher that is typically achieved with traditional calcium salt defluorination processes, without introducing new impurities. Under optimal adsorption conditions, the lanthanum–zirconium adsorbent exhibits a fluoride ion adsorption capacity of 193.4 mg/g in the leaching solution, surpassing that of many existing metal-based adsorbents. At the same time as the valuable metals, Li, Ni, and Co, are basically not adsorbed, the selective adsorption of fluoride ions can be achieved. Adsorption isotherm studies indicate that the adsorption process follows the Langmuir model, suggesting monolayer adsorption. The secondary adsorption process is primarily governed by chemical adsorption, and elevated temperatures facilitate the removal of fluoride ions. Kinetic studies demonstrate that the adsorption process is well described by the pseudo-second-order model. After desorption and regeneration with NaOH solution, the adsorbent still has a favorable fluoride removal performance, and the adsorption rate of fluoride ions can still reach 95% after four cycles of use. With its high capacity, rapid kinetics, and excellent selectivity, the adsorbent is highly promising for large-scale implementation. Full article

Silicon (Si) anodes offer ultrahigh theoretical capacity (~4200 mAh g⁻¹) for next-generation lithium-ion batteries but suffer from severe mechanical degradation due to repetitive volume expansion (>300%). Conventional electrode-centric strategies face scalability limitations, shifting focus to electrolyte engineering as a critical solution. This review synthesizes recent advances in liquid electrolyte design for stabilizing Si anodes, emphasizing three key pillars: (i) Lithium salts that enable anion-derived inorganic-rich solid electrolyte interphase (SEI) layers with high fracture toughness; (ii) Solvent systems including carbonates, ethers, and phosphonates, where fluorination and steric hindrance tailor SEI elasticity; (iii) Functional additives (F/B/Si-containing) that form mechanically compliant interphases and scavenge detrimental species. Innovative architectures—high-concentration electrolytes (HCEs), localized HCEs (LHCEs), and weakly solvating electrolytes—are critically assessed for their ability to decouple ion transport from volume strain. The perspective highlights the imperative of hybrid solid–liquid interfaces to enable commercially viable Si anodes. Full article

Nowadays, immersion cooling-based battery thermal management systems have demonstrated their effectiveness in controlling the temperature of lithium-ion batteries. While previous scientific research has primarily concentrated on traditional dielectric fluids such as mineral oil, the current research investigates the effectiveness of the dielectric fluid FC-40. A three-dimensional Computational Fluid Dynamics model of an eight-cell 18650 battery system was constructed using ANSYS Fluent 19.2 to examine the effect of cooling fluids (air, mineral oil, and FC-40), velocity of flow (0.01 m/s to 0.15 m/s), discharge rate (1C to 5C), and inlet/outlet size (2.5 mm to 3.5 mm) on thermal efficiency as well as pressure drop. The findings indicate that employing FC-40 as the dielectric fluid significantly reduces the peak cell temperature, with an absolute decrease of 2.80 °C compared to mineral oil and 15.10 °C compared to air. Furthermore, FC-40 achieves the highest uniformity with minimal hotspot. On the other hand, as the fluid velocity increases, the maximum temperature of the battery drops, reaching a minimum of 26 °C at a velocity of 0.15 m/s. Otherwise, at lower flow velocities, the pressure drop remains minimal, thereby reducing the pumping power consumption. Additionally, increasing the inlet and outlet diameter of the fluid directly improves cooling uniformity. Consequently, the temperature dropped by up to 4.3%. Finally, the findings demonstrate that elevated discharge rates contribute to increased heat dissipation but adversely affect the efficiency of the thermal management system. This study provides critical knowledge for the enhancement of battery thermal management systems based on immersion cooling using FC-40 as a dielectric. Full article

Near-complete (>99%) dissolution of lithium and cobalt was achieved by the leaching of black mass from spent (end-of-life) lithium-ion batteries (LiBs) using 4 M H₂SO₄ or HCl at 60 °C. Raising the temperature to 90 °C did not increase the overall extraction of lithium or cobalt, but it increased the rate of extraction. At 60 °C, 2 M H₂SO₄ or 2 M HCl performed similarly to the 4 M H₂SO₄/HCl solution, although extractions were lower using 1 M H₂SO₄ or HCl (~95% and 98%, respectively). High extractions were also observed by leaching in low pulp density (15 g/L) at 60 °C with 2 M CH₂ClCOOH. Leaching was much slower with hydrogen peroxide reductant concentrations below 0.5 mol/L, with cobalt extractions of 90–95% after 3 h. Pulp densities of up to 250 g/L were tested when leaching with 4 M H₂SO₄ or HCl, with the stoichiometric limit estimated for each test based on the metal content of the black mass. Extractions were consistently high, above 95% for Li/Ni/Mn/Cu with a pulp density of 150 g/L, dropping sharply above this point because of insufficient remaining acid in the solution in the later stages of leaching. The final component of the test work used leaching parameters identified in the previous experiments as producing the largest extractions, and just sulphuric acid. A seven-stage semi-continuous sulphuric acid leach at 60 °C of black mass from LiBs that had undergone an oxidising roast (2h in a tube furnace at 500 °C under flowing air) to remove binder material resulted in high (93%) extraction of cobalt and near total (98–100%) extractions of lithium, nickel, manganese, and copper. Higher cobalt extraction (>98%) was expected, but a refractory spinel-type cobalt oxide, Co₃O₄, was generated during the oxidising roast as a result of inefficient aeration, which reduced the extraction efficiency. Full article

In the coming decades, anticipated population growth is projected to escalate the demand for essential resources such as NaCl, KCl, and LiCl, which are critical for human consumption, agriculture, and battery production. A substantial proportion of these salts is produced from brines using solar evaporation ponds. This article presents a one-dimensional surrogate mathematical model of an ideal solar evaporation pond working at a steady state. The ideal pond considers only water evaporation, with a uniform evaporation rate per unit area. The model’s equation, or the ideal solar evaporation law, allows calculating the ion concentration profile in an ideal pond just given the feed and discharge concentrations. The validation of the law was conducted with industrial data collected in the year 2023 in a lithium recovery plant throughout 15 ponds in series at the Salar de Atacama, Chile. The results verified that the model could accurately predict the monthly concentration profiles (R² in the range 0.9646 to 0.9864) if lithium does not precipitate in the pond. The model provides accurate values of pond inventories and area requirements for designing stages. The model’s relevance extends beyond the lithium industry to encompass any solar evaporation processes for salt recovery or solution concentration. Full article

The recent increase in end-of-life (EoL) lithium-ion batteries (LiBs) has become a significant concern worldwide. Most studies in the literature have primarily focused on recovering cathode active metals from black mass (BM), whereas the separation of anode–cathode foils, plastics, and casing metals which are the essential components of LiBs has received relatively little attention. To reduce costs and maximize the recovery of valuable metals in subsequent hydrometallurgical or pyrometallurgical processes, EoL LiBs require appropriate pre-treatment. This study aims to scrape off the BM adhering to the electrode foils resulting from gradual crushing and subsequently separate the plastics and copper (Cu) from other metals through a two-step selective flotation process. The results demonstrated that plastics, due to their natural hydrophobicity, could be effectively removed using a frother, achieving more than 95% recovery with less than 5% metallic contamination. Following plastic flotation, Cu particles were floated in the presence of 3418A, yielding a Cu concentrate containing 65.13% Cu with a recovery rate of 96.4%. Additionally, the aluminum (Al) content in the non-floating material, remaining in the cell, increased to approximately 77%. Full article

In lithium-ion batteries, the fracture of active particles that are under stress is a key cause of battery aging, which leads to a reduction in active materials, an increase in internal resistance, and a decay in battery capacity. A coupled electrochemical–thermal–mechanical model was established to study the concentration and stress distributions of negative electrode particles under different charging rates and ambient temperatures. The results show that during charging, the maximum lithium-ion concentration occurs on the particle surface, while the minimum concentration appears at the particle center. Moreover, as the temperature decreases, the concentration distribution of negative electrode active particles becomes more uneven. Stress analysis indicates that when charging at a rate of 1C and 0 °C, the maximum stress of particles at the negative electrode–separator interface reaches 123.7 MPa, while when charging at 30 °C, the maximum particle stress is 24.3 MPa. The maximum shear stress occurs at the particle center, presenting a tensile stress state, while the minimum shear stress is located on the particle surface, showing a compressive stress state. Finally, to manage the stress of active materials in lithium-ion batteries while charging for health maintenance, this study uses a DNN (Deep Neural Network) to predict the maximum shear stress of particles based on simulation results. The predicted indicators, MAE (Mean Absolute Error) and RMSE (Root Mean Square Error), are 0.034 and 0.046, respectively. This research is helpful for optimizing charging strategies based on the stress of active materials in lithium-ion batteries during charging, inhibiting battery aging and improving safety performance. Full article