Search Results (14)

In the wake of global energy transition and the “dual-carbon” goal, the rapid growth of electric vehicles has posed challenges for large-scale lithium-ion battery decommissioning. Retired batteries exhibit dual attributes of strategic resources (cobalt/lithium concentrations several times higher than natural ores) and environmental risks (heavy metal pollution, electrolyte toxicity). This paper systematically reviews pyrometallurgical and hydrometallurgical recovery technologies, identifying bottlenecks: high energy/lithium loss in pyrometallurgy, and corrosion/cost/solvent regeneration issues in hydrometallurgy. To address these, an integrated recycling process is proposed: low-temperature physical separation (liquid nitrogen embrittlement grinding + froth flotation) for cathode–anode separation, mild roasting to convert lithium into water-soluble compounds for efficient metal oxide separation, stepwise alkaline precipitation for high-purity lithium salts, and co-precipitation synthesis of spherical hydroxide precursors followed by segmented sintering to regenerate LiNi_1/3Co_1/3Mn_1/3O₂ cathodes with morphology/electrochemical performance comparable to virgin materials. This low-temperature, precision-controlled methodology effectively addresses the energy-intensive, pollutive, and inefficient limitations inherent in conventional recycling processes. By offering an engineered solution for sustainable large-scale recycling and high-value regeneration of spent ternary lithium ion batteries (LIBs), this approach proves pivotal in advancing circular economy development within the renewable energy sector. Full article

Deep eutectic solvents are widely employed in the recycling and reuse of spent lithium-ion battery cathode materials because of their non-toxicity, low cost, and recyclability. Although DESs have a high recovery rate for metals and are more environmentally friendly, they typically require a longer time or higher temperatures. High temperature and pressure considerably improve leaching efficiency in traditional aqueous systems; this study investigates whether the same is true in DES systems. The physicochemical properties of a DES composed of choline chloride (ChCl) and malonic acid (MA) (1:1) were measured before and after high-temperature and high-pressure treatments, along with their effects on the leaching efficiency of cathode materials for spent lithium-ion batteries (LIBs). The results show that after treatment, the 632.03 cm⁻¹ twisted vibration peak of C-O was red-shifted to 603 cm⁻¹ and the alkyl chain of the DES was lengthened, whereas the 1150.52 cm⁻¹ C-O peak was blue-shifted to 1219 cm⁻¹ and the hydrogen-bonding effect was weakened. At long reaction times, crystals appeared inside the DES. Over time, the crystals increased in size and became less dense, and the color of the material changed from clear to blue to green. After pressurization treatment, the conductivity of the DES increased considerably over its value at atmospheric pressure. The leaching efficiency of Li, Co, Ni, and Mn were 53.20, 47.24, 26.27, and 48.57%, respectively, at 3 h of leaching at atmospheric pressure. The leaching efficiency increased to 78.20, 79.74, 69.76, and 81.80%, respectively, after being pressurized at 3.3 MPa. On this basis, the reaction time was extended to 6 h, and the leaching efficiency of Li, Co, Ni, and Mn were 96.41, 97.62, 98.13, and 97.34%, respectively, trending towards complete leaching. The leaching efficiency of spent LIB cathode materials in DESs was considerably improved under pressurized conditions, providing an efficient method for recovering spent LIB cathode materials using DESs. Full article

Catalytic oxidation is widely recognized as a highly effective approach for eliminating highly toxic CO. The current challenge lies in designing catalysts that possess exceptional low-temperature activity and stability. In this work, we have prepared ultrafine platinum particles of ~1 nm diameter dispersed on a MgFe₂O₄ support and found that the addition of 3 wt.% FeO_x into the 3Pt/MgFe₂O₄ significantly improves its activity and stability. At an ultra-low temperature of 30 °C, the CO can be totally converted to CO₂ over 3FeO_x-3Pt/MgFe₂O₄. High and stable performances of CO-catalytic oxidation can be obtained at 60 °C on 3FeO_x-3Pt/MgFe₂O₄ over 35 min on-stream at WHSV = 30,000 mL/(g·h). Based on a series of characterizations including BET, XRD, ICP, STEM, H₂-TPR, XPS, CO-DRIFT, O₂-TPD and CO-TPD, it was disclosed that the relatively high activity and stability of 3FeO_x-3Pt/MgFe₂O₄ is due to the fact that the addition of FeO_x could facilitate the antioxidant capacity of Pt and oxygen mobility and increase the proportion of adsorbed oxygen species and the amounts of adsorbed CO. These results are helpful in designing Pt-based catalysts exhibiting higher activity and stability at low temperatures for the catalytic oxidation of CO. Full article

The removal of decabromodiphenyl ether (BDE 209), as a typical persistent organic pollutant (POP), is of worldwide concern. Mechanochemical (MC) processes are promising methods to degrade environmental pollutants, most of which use a single grinding reagent. The performance of MC processes with co-milling agents still needs to be further verified. In this study, an efficient MC treatment with combined utilization of lithium cobalt oxide (LiCoO₂) and iron (Fe) as co-milling reagents for BDE 209 degradation was investigated. The synchronous action of LiCoO₂ and Fe with a LiCoO₂/Fe/Br molar ratio of 1.5:1.67:1 and a ball-to-powder ratio of 100:1 led to almost thorough-paced abatement and debromination of BDE 209 within 180 min using a ball milling rotation speed of 600 rpm. The reduction in particle sizes and the destruction of crystal structure in mixture powders with the increase in milling time induced the enhanced degradation of BDE 209, as characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The X-ray photoelectron spectroscopy (XPS) characterization showed that the valence state of Co was converted from Co(III) to Co(II), and Fe(0) was changed to Fe(III) when treated with an MC process. This indicated that the reductive debromination of BDE 209 by Fe and the following oxidative degradation of debrominated products by LiCoO₂ were integrated in a concerted way. It proved the removal of BDE 209 via an MC treatment. The full breakage of C-Br and C-O bonds in BDE 209 was confirmed by Fourier transform-infrared spectrometry (FT-IR) spectra, and a possible abatement pathway was also proposed based on the identified intermediate products using gas chromatography–mass spectrometry (GC-MS). These obtained results indicated that a combination of LiCoO₂ and Fe as co-milling reagents is promising in the MC treatment of toxic halogenated pollutants like BDE 209. Full article

Toxicity, emissions and structural damage results on lithium-ion battery (LIB) thermal runaway triggered by the electrothermal method were performed in this work. The electrothermal triggering method was determined to study the thermal runaway behaviors of three types of commercial LIBs. The structural damage of the cathode material of the batteries after thermal runaway was observed by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). It was found that as the state of charge (SOC) of the battery increases, the lower the temperature at which thermal runaway occurs, and the more badly the structural damage of the electrode material after thermal runaway. Qualitative analysis of products from LIBs thermal runaway emissions was conducted by GC-MS, and the toxicity and formation mechanism of the emissions were analyzed in detail. Dozens of toxic substances were detected from the emissions after thermal runaway of batteries using Li_xNi_1/3Co_1/3Mn_1/3O₂ and LiCoO₂ as the cathode material, the types of toxic substances increase gradually with the increase in the SOC, while as for batteries using LiFePO₄ as the cathode material, most types of toxic substances were detected from 30% SOC. Full article

To improve the working conditions in underground mines and eliminate the risk of human casualties, patrol robots that can operate autonomously are necessary. This study developed an autonomous patrol robot for underground mines and conducted field experiments at underground mine sites. The driving robot estimated its own location and autonomously operated via encoders, IMUs, and LiDAR sensors; it measured hazards using gas sensors, dust particle sensors, and thermal imaging cameras. The developed autonomous driving robot can perform waypoint-based path planning. It can also automatically return to the starting point after driving along waypoints sequentially. In addition, the robot acquires the dust and gas concentration levels along with thermal images and then combines them with location data to create an environmental map. The results of the field experiment conducted in an underground limestone mine in Korea are as follows. The O₂ concentration was maintained at a constant level of 15.7%; toxic gases such as H₂S, CO, and LEL were not detected; and thermal imaging data showed that humans could be detected. The maximum dust concentration in the experimental area was measured to be about 0.01 mg/m³, and the dust concentration was highly distributed in the 25–35 m section on the environmental map. This study is expected to improve the safety of work by exploring areas that are dangerous for humans to access using autonomous patrol robots and to improve productivity by automating exploration tasks. Full article

We report two complexes [Cu(L^I)₂] (1) and [Cu(L^II)₂] (2) (HL^I = N-cyclohexyl-3-methoxysalicylideneimine, HL^II = N-cyclohexyl-3-ethoxysalicylideneimine). The ligands in both complexes are trans-1,5-N,O-coordinated, yielding a square planar CuN₂O₂ coordination core. The molecule of 1 is planar with two cyclohexyl groups oriented to the opposite sites of the planar part of a molecule, while the molecule of 2 is significantly bent with two cyclohexyl groups oriented to the same convex site of a molecule. It was established that both complexes in MeOH absorb in the UV region due to intraligand transitions and LMCT. Furthermore, the UV-vis spectra of both complexes revealed two low intense shoulders in the visible region at about 460 and 520 nm, which were attributed to d–d transitions. Both complexes were predicted to belong to a fourth class of toxicity with the negative BBB property and positive gastrointestinal absorption property. According to the molecular docking analysis results, both complexes are active against all the applied SARS-CoV-2 proteins with the best binding affinity with Nsp 14 (N7-MTase), PLpro and Mpro. The obtained docking scores of complexes are either comparable to or even higher than those of the initial ligands. Complex 1 was found to be more efficient upon interaction with the applied proteins in comparison to complex 2. Ligand efficiency scores for the initial ligands, 1 and 2 were also revealed. Full article

Twenty-eight samples of {[(1-x-y) LiCo_0.3Cu_0.7](Al and Mg doped)]O₂}, xLi₂MnO₃, and yLiCoO₂ composites were synthesized using the sol–gel method. Stoichiometric weights of LiNO₃, Mn(Ac)₂⋅4H₂O, Co(Ac)₂⋅4H₂O, Al(NO₃)₃.H₂o, Mg(NO₃)₂⋅6H₂O, and Cu(NO₃)₂.H₂O for the preparation of these samples were applied. From this work, we confirmed the high performance of two samples, namely, Sample 18, including Al doped with structure “Li_1.5Cu_0.117Co_0.366Al_0.017Mn_0.5O₂” and Sample 17, including Mg doped with structure “Li_1.667Cu_0.1Mg_0.017Co_0.217Mn_0.667O₂”, compared with other compositions. Evidently, the used weight of cobalt in these two samples were lower compared with LiCoO₂, resulting in advantages in the viewpoint of cost and toxicity problems. Charge and discharge characteristics of the mentioned cathode materials were investigated by performing cycle tests in the range of 2.2–4.5 V. These types of systems can help to reduce the disadvantages of cobalt arising from its high cost and toxic properties. Our results confirmed that the performance of such systems is similar to that of pure LiCoO₂ cathode material, or greater in some cases. The biggest disadvantages of LiCoO₂ are its cost and toxic properties, typically making it cost around five times more to manufacture than when using copper. Full article

Lithium-ion batteries are known for their high efficiency for storing electrical energy, especially for hybrid vehicles. In this research, the development of mixture composites in the cathode electrode of LIBs has been discussed and designed based on ternary solid solutions. We have given a novel synthesis and method preparation of cathode electrode materials to reduce costs while increasing the efficiency and simultaneity for the future of these technologies. The major problem in the LIBs is related to LiCoO₂ as a popular cathode material that, although it has a high efficiency, is expensive and very toxic. Therefore, the usage of a lower weight of cobalt compared to the LiCoO₂ cathode material is economically advantageous for this research. Several samples of the (1-x-y) LiCo_1/3Ti_1/3Fe_1/3PO₄ xLi₂MnPO₄ and yLiFePO₄ system were synthesized via sol–gel experiments. Various stoichiometric amounts of the LiNO₃, Li₂MnPO₄, Mn (Ac)₂. 4H₂O, Co (Ac)₂.4H₂O, Ti(NO₃)₂.6H₂O and LiFePO₄ have been used for several compositions of chrome, manganese, cobalt and titanium in 28 samples of (1-x-y) LiCo_1/3Ti_1/3Fe_1/3PO₄. By using thermal characterization, five samples have been selected due to their conditions in viewpoints of capacity and cyclability as well as activation energy, which is one of the major factors. These composites exhibited fairly consistent charge/discharge curves during the electrochemical testing. From the viewpoint of the physical and chemical properties, among these samples, the Li_1.501Co_0.389Ti_0.055Fe_0.055Mn_0.501PO₄ structure has a high efficiency compared to other compositions. Full article

A challenge in developing high-performance lithium batteries requires a safe technology without flammable liquid electrolytes. Nowadays, two options can satisfy this claim: all-solid-state batteries and aqueous-electrolyte batteries. Commercially available Li-ion batteries utilize non-aqueous electrolytes (NAE) owing to a wide potential window (>3 V) that achieves high energy density but pose serious safety issues due to the high volatility, flammability, and toxicity of NAE. On the contrary, aqueous electrolytes are non-flammable, low-toxic, and have a low installation cost for humidity control in the production line. In this scenario, we develop a new aqueous rechargeable Li-ion full-cell composed of high-voltage cathode material as LiCoO₂ (LCO) and a safe nanostructured anode material as Li₂TiO₃ (LTO). Both pure-phase LTO and LCO nanopowders are prepared by hydrothermal route and their structural and electrochemical properties are studied in detail. Simultaneously, the electrochemical performances of these electrodes are tested in both half- and full-cell configurations in presence of saturated 1 mole L⁻¹ Li₂SO₄ aqueous electrolyte medium. Pt//LCO and Pt//LTO half-cells deliver high discharge capacities of 142 and 133 mAh g⁻¹ at 0.5 C rate with capacity retention of ~95% and 94% after 50 cycles with a Coulombic efficiency of 98.25% and 99.89%, respectively. The electrochemical performance of a LTO//LCO full cell is investigated for the first time. It reveals a discharge capacity of 135 mAh g⁻¹ at 0.5 C rate (50th cycle) with a capacity retention of 94% and a Coulombic efficiency of 99.7%. Full article

Lithium-ion batteries have led the revolution in portable electronic devices and electrical vehicles due to their high gravimetric energy density. In particular, layered cathode material Li(Ni_0.6Mn_0.2Co_0.2)O₂ (NMC 622) can deliver high specific capacities of about 180 mAh/g. However, traditional cathode manufacturing involves high processing costs and environmental issues due to the use of organic binder polyvinylidenfluoride (PVDF) and highly toxic solvent N-methyl-pyrrolidone (NMP). In order to overcome these drawbacks, aqueous processing of thick-film NMC 622 cathodes was studied using carboxymethyl cellulose and fluorine acrylic hybrid latex as binders. Acetic acid was added during the mixing process to obtain slurries with pH values varying from 7.4 to 12.1. The electrode films could be produced with high homogeneity using slurries with pH values smaller than 10. Cyclic voltammetry measurements showed that the addition of acetic acid did not affect the redox reaction of active material during charging and discharging. Rate capability tests revealed that the specific capacities with higher slurry pH values were increased at C-rates above C/5. Cells with laser structured thick-film electrodes showed an increase in capacity by 40 mAh/g in comparison to cells with unstructured electrodes. Full article

Lithium manganite, Li₂MnO₃, is an attractive cathode material for rechargeable lithium ion batteries due to its large capacity, low cost and low toxicity. We employed well-established atomistic simulation techniques to examine defect processes, favourable dopants on the Mn site and lithium ion diffusion pathways in Li₂MnO₃. The Li Frenkel, which is necessary for the formation of Li vacancies in vacancy-assisted Li ion diffusion, is calculated to be the most favourable intrinsic defect (1.21 eV/defect). The cation intermixing is calculated to be the second most favourable defect process. High lithium ionic conductivity with a low activation energy of 0.44 eV indicates that a Li ion can be extracted easily in this material. To increase the capacity, trivalent dopants (Al³⁺, Co³⁺, Ga³⁺, Sc³⁺, In³⁺, Y³⁺, Gd³⁺ and La³⁺) were considered to create extra Li in Li₂MnO₃. The present calculations show that Al³⁺ is an ideal dopant for this strategy and that this is in agreement with the experiential study of Al-doped Li₂MnO₃. The favourable isovalent dopants are found to be the Si⁴⁺ and the Ge⁴⁺ on the Mn site. Full article

With the rapid increase in production of lithium-ion batteries (LIBs) and environmental issues arising around the world, cathode materials, as the key component of all LIBs, especially need to be environmentally sustainable. However, a variety of life cycle assessment (LCA) methods increase the difficulty of environmental sustainability assessment. Three authoritative LCAs, IMPACT 2002+, Eco-indicator 99(EI-99), and ReCiPe, are used to assess three traditional marketization cathode materials, compared with a new cathode model, FeF₃(H₂O)₃/C. They all show that four cathode models are ranked by a descending sequence of environmental sustainable potential: FeF₃(H₂O)₃/C, LiFe_0.98Mn_0.02PO₄/C, LiFePO₄/C, and LiCoO₂/C in total values. Human health is a common issue regarding these four cathode materials. Lithium is the main contributor to the environmental impact of the latter three cathode materials. At the midpoint level in different LCAs, the toxicity and land issues for LiCoO₂/C, the non-renewable resource consumption for LiFePO₄/C, the metal resource consumption for LiFe_0.98Mn_0.02PO₄/C, and the mineral refinement for FeF₃(H₂O)₃/C show relatively low environmental sustainability. Three LCAs have little influence on total endpoint and element contribution values. However, at the midpoint level, the indicator with the lowest environmental sustainability for the same cathode materials is different in different methodologies. Full article

In this paper, the application of recycled Li-ion battery spent cathodes (LIB-SC) combined with a NaHCO₃/H₂O₂ system is presented for the first time in the literature as an alternative for the degradation of potentially toxic organic molecules. The model pollutant choice was methylene blue molecule. The spent cathode composition corresponds to LiCoO₂, which was proved by the XRD and EDX. Regarding the decolorization of methylene blue solution, the addition of NaHCO₃, in comparison with only H₂O₂, reduces the complete decolorization time by 96%. This reduction occurs because the radical ${\mathrm{CO}}_3^{.}$ is more stable than OH. In this way, the application of the system proposed in this article is aimed at solving two major global problems: the disposal of cell phone batteries and the pollution of liquid effluents. Full article