Search Results (110)

This study investigates the selective dissolution of manganese from a manganiferous iron ore using nitric acid (HNO₃) in the presence of various organic reductants. A series of leaching experiments was performed to evaluate the effects of temperature, reductant type, and leaching time on Mn recovery, with particular emphasis on biomass (horse dung) and tartaric acid as novel reducing agents. The dissolution behaviour of Fe, Mn, Mg, Ca, and Al was systematically examined, revealing that Mn extraction was strongly enhanced in the presence of reductants, while Fe dissolution remained below 10% under all conditions. The maximum Mn dissolution exceeded 90% at 90 °C using biomass and reached nearly 85%–90% with tartaric acid at elevated temperatures. Kinetic studies were conducted by applying reaction order models and the shrinking core model. The results indicated that Mn dissolution in HNO₃ medium is predominantly controlled by surface chemical reaction, with Arrhenius analysis yielding activation energies of 27.74 kJ/mol for biomass and 21.26 kJ/mol for tartaric acid. These relatively low values confirm the efficiency of organic reductants in facilitating Mn reduction and dissolution. To sum up, comparison of reductant efficiency revealed that, at the lowest concentrations, the dissolution of Mn followed the sequence glucose > sucrose > oxalic acid > tartaric acid > maleic acid > biomass > citric acid > acetic acid. At the highest concentrations, the trend shifted, with citric acid emerging as the most effective, followed by tartaric acid > oxalic acid > glucose > sucrose > maleic acid > biomass > acetic acid. Full article

Background: Thiabendazole (TBZ), a benzimidazole with established antifungal and anthelmintic properties, has also been reported to exert antiangiogenic effects relevant to tissue remodeling and chronic inflammatory microenvironments. The present study examined how manganese coordination and cyclodextrin modify the dissolution behavior and endothelial activity of TBZ. Methods: Antiangiogenic potential was assessed through a human umbilical vein endothelial cells (HUVECs) scratch-wound migration assay. Dissolution profiles of TBZ, manganese–thiabendazole (MnTBZ), and MnTBZ/monochlorotriazynil-β-cyclodextrin (MCT-β-CD) formulation were evaluated under biorelevant pH conditions (1.2, 4.5, 6.8, 7.4) using the paddle method. Results: TBZ displayed a more rapid and extensive dissolution at pH 1.2, compared to MnTBZ. Partial dissociation at pH 4.5 modestly improved TBZ availability, while dissolution remained minimal at neutral pH. MCT-β-CD enhanced the solubility of MnTBZ at pH ≥ 6.8. In agreement with these profiles, TBZ exerted the strongest inhibition of endothelial migration, followed by MnTBZ/MCT-β-CD and MnTBZ. Conclusions: Manganese coordination and cyclodextrin formulation modulate both the dissolution behavior and endothelial migration-inhibitory activity of TBZ, suggesting that such formulation approaches may influence the delivery-related and functional properties of benzimidazole derivatives. Full article

Nowadays, spent batteries are considered a secondary and potential resource to meet the growing demand for lithium, a critical element widely used in the manufacturing of electric vehicles. Therefore, this work presents a hydrometallurgical method for extracting lithium from Nickel–Manganese–Cobalt (NMC) batteries. Citric (${\mathrm{C}}_6{\mathrm{H}}_8{\mathrm{O}}_7$) and oxalic (${\mathrm{C}}_2{\mathrm{H}}_2{\mathrm{O}}_4$) acids were used as leaching agents, both of which are cataloged as environmentally friendly organic compounds. To comprehend the chemical interactions between citrate ($\mathrm{c}\mathrm{i}\mathrm{t}$), oxalate ($\mathrm{o}\mathrm{x}$) and metallic ions, a thermodynamic analysis is presented. According to this analysis, both ions were effective in dissolving lithium; however, the experimental studies demonstrated that oxalate ensured a selective process and achieved complete lithium dissolution under the experimental conditions 1 M C₂H₂O₄, 50 g/L, 60 °C, and 60 min, with a mechanically treated sample (milling time 8 min at 1000 rpm). In this process, the other metals present in the sample, such as cobalt, nickel, and manganese, formed insoluble species with oxalate, allowing their recovery in subsequent stages. Therefore, this investigation provides a proficient methodology for battery recycling, emphasizing sustainable practices. Full article

The escalating production and use of lithium-ion batteries (LIBs) have led to a pressing need for efficient and sustainable methods for recycling valuable metals such as cobalt, nickel, manganese, and lithium from spent cathode materials. Traditional hydrometallurgical leaching approaches, based on mineral acids, face significant limitations, including high reagent consumption, secondary pollution, and poor selectivity. In recent years, deep eutectic solvents (DESs) and ionic liquids (ILs) have emerged as innovative, environmentally benign alternatives, offering tunable physicochemical properties, enhanced metal selectivity, and potential for reagent recycling. This review provides a comprehensive analysis of the current state and prospects of leaching LIB cathode materials using DES and ILs. We summarize the structural diversity and composition of common LIB cathodes, highlighting their implications for leaching strategies. The mechanisms, efficiency, and selectivity of metal dissolution in various DES- and IL-based systems are critically discussed, drawing on recent advances in both laboratory and real-sample studies. Special attention is given to the unique extraction mechanisms facilitated by complexation, acid–base, and redox interactions in DES and ILs, as well as to the effects of key operational parameters. A comparative analysis of DES- and IL-based leaching is presented, with discussion of their advantages, challenges, and industrial potential. While DES offers low toxicity, biodegradability, and cost-effectiveness, it may suffer from limited solubility or viscosity issues. Conversely, ILs provide remarkable tunability and metal selectivity but are often hampered by higher costs, viscosity, and environmental concerns. Finally, the review identifies critical bottlenecks in upscaling DES and IL leaching technologies, including long-term solvent stability, metal recovery purity, and economic viability. We also highlight research priorities that emphasize applying circular hydrometallurgy and life-cycle assessment to improve the sustainability of battery recycling. Full article

This study investigates the valorisation of piscindustrial by-products, specifically fishbones from mackerel, horse-mackerel, and sardines, as sustainable sources of multi-mineral ingredients (MMIs) for future dietary supplementation. Ground fishbone powders were first analysed for moisture content and total ash to establish baseline composition. Following these preliminary assessments, the samples underwent mineral profiling using microwave plasma atomic emission spectroscopy (MP-AES), enabling quantification of calcium, phosphorus, magnesium, iron, zinc, sodium, potassium, copper, lead, cadmium, selenium, chromium, tin, manganese, and mercury. All three species yielded high concentrations of essential minerals, supporting their relevance as upcycled nutritional resources. A sardine-based capsule formulation was developed and compared with a commercial calcium supplement through 240 min dissolution testing. While calcium release values differed significantly from 75 min onward, both formulations exhibited similar dissolution profile shapes, despite differing dosage forms. Statistical analysis confirmed time- and formulation-dependent effects, with the sardine capsule demonstrating enhanced calcium bioaccessibility in later phases (95.26 ± 10.11 vs. 78.79 ± 5.39 mg). This work contributes to the advancement of the United Nations Sustainable Development Goals (SDGs), particularly SDG 3, SDG 12, and SDG 14. By transforming marine waste into health-promoting ingredients, and enabling revenue streams for ocean-cleaning charities, this initiative exemplifies circular innovation at the interface of nutrition, sustainability, and marine stewardship. Full article

In the nuclear industry, the decontamination of nuclear metallic structures is an essential process to reduce radiation exposure during maintenance or dismantling. The oxide layer, such as chromium (III) oxide (Cr₂O₃), formed on stainless steel and nickel-based alloys, contributes significantly to surface radioactivity by trapping radioactive contaminants. To address this, permanganic acid (HMnO₄) has proven to be a promising oxidizing agent for dissolving these oxide layers—particularly chromium oxide—on stainless steel and nickel-based alloys. In this study, HMnO₄ was synthesized via ion exchange using AmberLite IRN97 H resin and potassium permanganate (KMnO₄). The optimized process yielded a highly acidic solution (pH~1.6) with potassium concentrations below 0.1 ppm, indicating near-complete exchange efficiency. Dissolution kinetics were investigated at HMnO₄ concentrations ranging from 240 to 1920 ppm and temperatures from 30 °C to 80 °C. At a constant temperature, increasing HMnO₄ concentration significantly improved Cr dissolution, with up to 31% of total chromium solubilized after 33 h. Lower temperatures favored higher dissolution efficiency, likely due to improved thermal stability of HMnO₄. For durations shorter than 4 h, the influence of temperature was limited compared to the effect of acid concentration. To assess post-treatment options, HMnO₄ decomposition was studied using oxalic acid (H₂C₂O₄) at 80 °C. Results showed that a minimum H₂C₂O₄/HMnO₄ molar ratio above 2.75 was necessary to achieve effective reduction while preventing MnO₂ precipitation. However, even under strongly acidic conditions and with a large excess of reductant, Mn²⁺ yields remained below 55%, suggesting that thermal degradation of oxalic acid and possible formation of undetected manganese species limited the reduction process. Full article

Owing to the inherent safety, environmental friendliness, and high theoretical capacity (820 mAh g⁻¹) of zinc metal, aqueous zinc-ion batteries (AZIBs) have emerged as up-and-coming alternatives to organic lithium-ion batteries. However, the insufficient electrochemically active sites, poor structural stability, and severe interfacial side reactions of cathode materials have always been key challenges, restricting battery gravimetric energy density and cycling stability. This article systematically reviews current mainstream AZIB cathode material systems, encompassing layered manganese- and vanadium-based metal oxides, Prussian blue analogs, and emerging organic polymers. It focuses on analyzing the energy storage mechanisms of different material systems and their structural evolution during Zn²⁺ (de)intercalation. Furthermore, mechanisms of innovative strategies for improving cathodes are thoroughly examined here, such as nanostructure engineering, lattice doping control, and surface coating modification, to address common issues like structural degradation, manganese/vanadium dissolution, and interface passivation. Finally, this article proposes future research directions: utilizing multi-scale in situ characterization to elucidate actual reaction pathways, constructing artificial interface layers to suppress side reactions, and optimizing full-cell design. This review provides a new perspective for developing practical AZIBs with high specific energy and long lifespans. 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 response to the pressing environmental challenges posed by electrolytic manganese residue (EMR) and red mud (RM), this study proposes an innovative cementitious material technology for the synergistic co-utilization of these industrial wastes. By employing steel slag (SS) as a calcium-rich skeleton, the system effectively immobilizes sulfates from EMR and alkalinity from RM, converting hazardous wastes into value-added construction materials. Through orthogonal experimentation, an optimal mix proportion was established—30% RM, 20% EMR, and 50% SS at a water-to-binder ratio of 0.28—which achieved a 28-day compressive strength of 20.40 MPa, meeting relevant industry standards for auxiliary cementitious materials. Microstructural analysis unveiled a multi-stage alkali-sulfate synergistic activation mechanism: (1) the high alkalinity derived from RM rapidly activates the dissolution of aluminosilicate phases in both SS and EMR; (2) sulfate ions released from EMR promote extensive formation of ettringite (AFt), enhancing early-age structural integrity; and (3) calcium ions from SS facilitate the development of a dense C-S-H gel matrix, which serves as the primary binding phase. More profoundly, this process exemplifies a self-stabilizing waste-to-resource conversion mechanism, whereby harmful constituents (sulfates and free alkalis) are constructively incorporated into stable hydration products. This work not only elucidates a coherent scientific framework for the safe and efficient reclamation of multi-source solid wastes, but also demonstrates a scalable and ecologically viable pathway for million-ton-scale valorization of EMR and RM. Furthermore, it presents feasibility insights for the application of high-dosage steel slag-based material systems, thereby unifying significant environmental and economic advantages. Full article

Aqueous zinc-ion batteries (ZIBs) have emerged as a promising candidate for large-scale energy storage due to their inherent safety, low cost, and environmental friendliness. However, manganese dioxide (MnO₂)-based cathodes, which are widely studied for ZIBs owing to their high theoretical capacity and low cost, face severe capacity fading issues that hinder the commercialization of ZIBs. This performance degradation mainly stems from the weak van der Waals forces between MnO₂ layers leading to structural collapse during repeated Zn²⁺ insertion and extraction; it is also exacerbated by irreversible Mn dissolution via Mn³⁺ disproportionation that depletes active materials, and further aggravated by dynamic electrolyte pH fluctuations promoting insulating zinc hydroxide sulfate (ZHS) formation to block ion diffusion channels. To address these interconnected challenges, in this study, a synergistic strategy was developed combining crystal engineering and pH buffer regulation. We synthesized three MnO₂ polymorphs (α-, δ-, γ-MnO₂), identified δ-MnO₂ with flower-like microspheres as optimal, and introduced sodium dihydrogen phosphate (NaH₂PO₄) as a pH buffer (stabilizing pH at 2.8 ± 0.2). The modified electrolyte improved δ-MnO₂ wettability (contact angle of 17.8° in NaH₂PO₄-modified electrolyte vs. 26.1° in base electrolyte) and reduced charge transfer resistance (Rct = 78.17 Ω), enabling the optimized cathode to retain 117.25 mAh g⁻¹ (82.16% retention) after 2500 cycles at 1 A g⁻¹. This work provides an effective strategy for stable MnO₂-based ZIBs, promoting their application in renewable energy storage. Full article

The karst landscape of Trenggalek Regency, located in several sub-districts including Dongko, Kampak, and Watulimo, is shaped by the Wonosari Formation and is characterized by springs and underground rivers. Due to water scarcity in the region, local communities heavily depend on these natural water sources. This study assesses the groundwater quality of 16 springs and 20 underground rivers to evaluate their suitability for consumption and associated health risks. Using the groundwater quality index (GWQI), human health risk assessment (HHRA), and statistical methods, various physicochemical parameters were analyzed, including pH, total dissolved solids (TDS), electrical conductivity (EC), and concentrations of iron (Fe²⁺), manganese (Mn²⁺), calcium carbonate (CaCO₃), and sulfate (SO₄). Water generally meets the World Health Organization standards for safe drinking. However, correlation analysis reveals notable mineral dissolution and possible anthropogenic influence. TDS strongly correlates with EC (r = 0.97), while Fe²⁺ shows significant relationships with Mn and TDS. Conversely, CaCO₃ shows a negative correlation with EC and TDS, suggesting alternative sources beyond rock weathering. The HHRA indicates higher non-carcinogenic health risks from Fe²⁺ contamination in underground rivers compared to springs. The study’s novelty comes in its integrated assessment of groundwater quality and health hazards in Trenggalek’s karst region, which uses GWQI, HHRA, and statistical analysis to show geochemical interactions and highlight iron-related health issues in underground rivers. Full article

Rechargeable aqueous Zn-MnO₂ batteries are positioned as a highly promising candidate for next-generation energy storage, owing to their compelling combination of economic viability, inherent safety, exceptional capacity (with a theoretical value of ≈308 mAh·g⁻¹), and eco-sustainability. However, this system still faces multiple critical challenges that hinder its practical application, primarily including the ambiguous energy storage reaction mechanism (e.g., unresolved debates on core issues such as ion transport pathways and phase transition kinetics), dendrite growth and side reactions (e.g., the hydrogen evolution reaction and corrosion reaction) on the metallic Zn anode, inadequate intrinsic electrical conductivity of MnO₂ cathodes (≈10⁻⁵ S·cm⁻¹), active material dissolution, and structural collapse. This review begins by systematically summarizing the prevailing theoretical models that describe the energy storage reactions in Zn-Mn batteries, categorizing them into the Zn²⁺ insertion/extraction model, the conversion reaction involving MnO_x dissolution–deposition, and the hybrid mechanism of H⁺/Zn²⁺ co-intercalation. Subsequently, we present a comprehensive discussion on Zn anode protection strategies, such as surface protective layer construction, 3D structure design, and electrolyte additive regulation. Furthermore, we focus on analyzing the performance optimization strategies for MnO₂ cathodes, covering key pathways including metal ion doping (e.g., introduction of heteroions such as Al³⁺ and Ni²⁺), defect engineering (oxygen vacancy/cation vacancy regulation), structural topology optimization (layered/tunnel-type structure design), and composite modification with high-conductivity substrates (e.g., carbon nanotubes and graphene). Therefore, this review aims to establish a theoretical foundation and offer practical guidance for advancing both fundamental research and practical engineering of Zn-manganese oxide secondary batteries. Full article

The surging demand for lithium-ion batteries (LIBs) has intensified the need for sustainable recovery of critical metals such as lithium, manganese, cobalt, and nickel from spent cathodes. While conventional hydrometallurgical and pyrometallurgical methods are widely used, they involve high energy consumption, hazardous waste generation, and complex processing steps, underscoring the urgency of developing eco-friendly alternatives. This study presents a novel, water-enhanced deep eutectic solvent (DES) system composed of choline chloride and D-glucose for the efficient leaching of valuable metals from spent LiMn-based battery cathodes. The DES was synthesized under mild conditions and applied to dissolve cathode powder, with leaching performance optimized by varying temperature and duration. Under optimal conditions (100 °C, 24 h), exceptional recovery efficiencies were achieved: 98.9% for lithium, 98.4% for manganese, and 71.7% for nickel. Material characterization using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and inductively coupled plasma mass spectrometer (ICP-MS) confirm effective phase dissolution and metal release. Although this DES system requires relatively higher temperature and longer reaction time compared to traditional acid leaching, it offers clear advantages in terms of non-toxicity, biodegradability, and elimination of strong oxidizing agents. These results demonstrate the potential of water-enhanced choline chloride–glucose DES as a green alternative for future development in sustainable battery recycling, supporting circular economy objectives. Full article

The exponential growth of global electric vehicle deployment has precipitated a critical need for the sustainable recycling of end-of-life lithium-ion batteries (LIBs), particularly nickel–cobalt–manganese (NCM) ternary cathodes, which dominate the retired battery stream. This study establishes an integrated Aspen Plus-based hydrometallurgical process model, focusing on “acid dissolution–LiOH precipitation–electrolysis” for closed-loop NCM recycling. Gibbs reactor-based dissolution kinetics is used for selective metal leaching (achieving > 99% efficiency at 185 kg/h acid flow), the thermodynamic prioritization of sequential hydroxide precipitation (Co → Ni → Mn at 10–60 kg/h LiOH), and the electrochemical regeneration of LiOH/H₂SO₄ from Li₂SO₄ (70.01 kg/h LiOH at 0.8 conversion). Material balance analysis confirms a net production of 10.01 kg LiOH per 100 kg of NCM feedstock with 41.87 kg of acid consumption, while the energy of electrolysis power is 452.96 kW at 6 V/1360 A/m². This work provides a techno-economic framework for industrial-scale battery recycling. Full article

Exposure of LIB materials to ambient conditions with some level of humidity, either accidentally owing to imperfect fabrication or cell damage, or deliberately due to battery opening operations for analytical or recycling purposes, is a rather common event. As far as humidity-induced damage is concerned, on the one hand the general chemistry is well known, but on the other hand, concrete structural details of these processes have received limited explicit attention. The present study contributes to this field with an investigation centered on the use of Raman spectroscopy for the assessment of structural modifications using common lithium iron phosphate (LFP) and nickel–cobalt–manganese/lithium–manganese oxide (NCM-LMO) cathodes. The impact of humidity has been followed through the observation of differences in Raman bands of pristine and humidity-exposed cathode materials. Vibrational spectroscopy has been complemented with morphological (SEM), chemical (EDS), and electrochemical analyses. We have thus pinpointed the characteristic morphological and compositional changes corresponding to corrosion and active material dissolution. Electrochemical tests with cathodes reassembled in coin cells allowed for the association of specific capacity losses with humidity damaging. Full article