Resource recovery and regeneration strategies for spent lithium-ion batteries: Toward sustainable high-value cathode materials.

Traditional cathode recycling methods have become outdated amid growing concerns for high-value output and environmental friendliness in spent Li-ion battery (LIB) recycling. Our study presents a closed-loop approach that involves selective sulfurization roasting, water leaching, and regeneration, efficiently transforming spent ternary Li batteries (i.e., NCM) into high-performance cathode materials. By combining experimental investigations with density functional theory (DFT) calculations, we elucidate the mechanisms within the NCM-C-S roasting system, providing a theoretical foundation for selective sulfidation. Utilizing in situ X-ray diffraction techniques and a series of consecutive experiments, the study meticulously tracks the evolution of regenerating cathode materials that use transition metal sulfides as their primary raw materials. The Li-rich regenerated NCM exhibits exceptional electrochemical performance, including long-term cycling, high-rate capabilities, reversibility, and stability. The closed-loop approach highlights the sustainability and environmental friendliness of this recycling process, with potential applications in other cathode materials, such as LiCoO2 and LiMn2O4. Compared with traditional methods, this short process approach avoids the complexity of leaching, solvent extraction, and reverse extraction, significantly increasing metal utilization and Li recovery rates while reducing pollution and resource waste.

Innovative methodology for comprehensive utilization of arsenic-bearing neutralization sludge.

Arsenic-bearing neutralization (ABN) sludge is a classical hazardous waste commonly found in nonferrous metallurgy. However, the current storage of these hazardous wastes not only has to pay costly hazardous waste taxes but also poses significant risks to both the environment and human health. To address these issues and achieve the comprehensive utilization and minimization of ABN sludge, this study proposes a new combined process. The process involves selective reduction roasting, leaching, and carbonation, through which, the arsenate and gypsum in the ABN sludge were recovered in the form of As(s), high-purity CaCO3, and H2S. The selective reduction behaviors of arsenate and gypsum were investigated through thermodynamic analysis and roasting experiments. The results indicated that the 95.35 % arsenate and 96.55 % gypsum in the sludge were selectively reduced to As4(g) and CaS at 950 °C by carbothermic reduction. The As4(g) was condensed to As(s) and enriched in the dust (As, 96.78 wt %). In the leaching process, H2S gas was adopted to promote the leaching of CaS, and resulted in 97.41 % of CaS in the roasted product was selectively leached in the form of Ca(HS)2, leading to a 74.11 % reduction in the weight of the ABN sludge. Then, the Ca(HS)2 was subjected to capture CO2 for the separation of Ca2+ and S2-. The result depicted that 99.69 % of Ca2+ and 99.12 % of S2- were separated as high-purity (99.12 wt %) CaCO3 and H2S (24.89 vol %) by controlling the terminal carbonation pH to below 6.55. The generated H2S can be economically converted to sulfur by the Clause process. The whole process realized the comprehensive resource recovery and the minimization of the sludge, which provides an alternative solution for the clean treatment of hazardous ABN waste.

New Insight into Elastic Mechanical Properties and Anisotropies of Crystal Defect α-Quartz from DFT Calculation.

To reveal the cleavage mechanism of α-quartz in the grinding process of nonferrous metal ores, mechanical and charge properties of α-quartz crystals are investigated using the density functional theory. Based on the elastic constant matrix, the bulk and shear moduli were calculated before and after the α-quartz with oxygen atom defects. The results show that the ratios of bulk and shear moduli (B/G) were 0.87 and 0.95, respectively, which indicated that at the same stress level, it was easier to fracture without O-vacancy defects than with O-vacancy defects. The mapping surfaces indicated that the O-vacancy defect increased the bulk-, shear-, and Young's moduli, and Poisson ratio while decreasing the hardness. The anisotropy index (AL and AU) was calculated which illustrated that the O-vacancy can result in an increased anisotropy; meanwhile, the bulk anisotropy index (AB) increased strongly about two times. The anisotropy analysis shows the dominance crystal cleavage of the (011) plane in the shear stress and the dominance crystal cleavage of the (111) plane in the normal stress. The electron localization function α-quartz show that the O-vacancy defect can decrease the Si-Si length from 3.703 to 2.442 Å, which indicated that the O-vacancy formed the new covalent bonds between silicon atoms. Our work provided a systematic approach containing the mechanical, anisotropic, and electronic properties of mineral crystals to explain the cleavage behavior of crystals.

Closed-loop recycling of spent lithium-ion batteries based on selective sulfidation: An unconventional approach.

The facile recycling of spent lithium-ion batteries (LIBs) has attracted considerable attention because of its great importance to environmental protection and resource utilization. A novel process is developed for cyclic utilization of spent LiNixCoyMnzO2 (NCM) batteries. The spent NCM was converted into water-soluble Li2CO3, acid-dissolved MnO, and nickel-cobalt sulfides through selective sulfidation, based on roasting condition optimization and thermodynamic calculation. More than 98 % of lithium is extracted preferentially from calcined NCM through water leaching, and over 99 % of manganese is extracted selectively from water leaching residue with H2SO4 solution of 0.4 mol/L in the absence of additional reductant. The nickel and cobalt sulfides were concentrated into the leaching residue without metal impurities. The obtained Li2CO3, MnSO4, and nickel-cobalt sulfides can be regenerated as new NCM, showing good electrochemical performance, and its discharge capacity is 169.8 mAh/g at 0.2C. After 100 cycles at 0.2C, the discharge specific capacity can still be maintained at 143.24 mAh/g, and its capacity retention ratio is as high as 92  %. An environmental assessment and economic evaluation indicate that the process is an economical and eco-friendly approach for green recycling of spent LIBs.

Recovery of zinc and extraction of calcium and sulfur from zinc-rich gypsum residue by selective reduction roasting combined with hydrolysis.

A novel process that includes selective reduction roasting followed by hydrolysis was proposed in this work to recover zinc, and efficiently extract calcium and sulfur from hazardous zinc-rich gypsum residue (ZGR) waste for high-purity of CaCO3 and sulfur production. The selective reduction behaviors of ZGR during the reduction roasting were investigated in detail based on thermodynamic analysis and roasting experiments. The effect of roasting temperature, carbon dosage and time on the selective reduction of ZGR was comprehensively investigated, and the results indicated that ZnO and CaSO4 in the ZGR can be selectively reduced to Zn(g) and CaS, respectively. The volatile Zn(g) was oxidized to ZnO and enriched in the dust, which can be used as a secondary zinc resource. Moreover, the hydrolysis behaviors and leaching kinetic of CaS during hydrolysis were studied intensively. Results depicted that in the H2S-H2O system, the CaS in the roasted product can be selectively and efficiently dissolved into the leachate. Furthermore, the kinetic analysis revealed that the hydrolysis of CaS conformed to the internal diffusion reaction control model in the shrinking core model and the apparent activation energy Ea = -12.02 kJ/mol. The obtained hydrolysate with low impurities could be used to capture CO2 for the production of high-purity sulfur and CaCO3. Iron and other impurities in the roasted product were concentrated into the leaching slag in the form of metallic iron and akermanite. The whole process realized the recovery of zinc, and the selective and effective extraction of calcium and sulfur, which could provide an alternative process for the large-scale treatment of these hazardous wastes.

Facile separation and regeneration of LiFePO4 from spent lithium-ion batteries via effective pyrolysis and flotation: An economical and eco-friendly approach.

The facile recycling of spent lithium-ion batteries (LIBs) has attracted much attention because of its great significance to the environmental protection and resource utilization. Hydrometallurgical process is the most common method for recycling spent LIBs, but it is difficult to economically recover spent LiFePO4 batteries, because of the complicated metal separation process and low added value of its products. Herein, a novel and facile approach has been developed to achieve the direct regeneration of LiFePO4 from spent LIBs. By employing a flotation process after effective pyrolysis, it is found that 91.57% of LiFePO4 can be recovered from spent LIBs. Different surface hydrophobicity of cathode and anode active materials could be achieved via the selective adsorption of causticized soluble starch on the surfaces of spent LiFePO4, which effectively enhances the separation performance in flotation process. The recovered LiFePO4 barely contains metal impurities, which can be directly regenerated as new LiFePO4 materials with the first discharge capacity of 161.37 mAh/g, and their capacity retention is as high as 97.53% after 100 cycles at 0.2C. A technology assessment and economic evaluation indicate the developed regeneration approach of LiFePO4 is environmentally and economically feasible, which avoids the complex element separation process and achieves the facile recycling of spent LiFePO4.

Production and resource utilization of flue gas desulfurized gypsum in China - A review.

Flue gas desulfurized gypsum (FGD gypsum), mainly originates from thermal power plants, smelters, and large-scale enterprise boilers. This article reviews the production in China and the latest beneficial utilizations of FGD gypsum. China is a large coal-consuming country and has always had serious SO2 emissions. Therefore, the Chinese government has implemented a large number of desulfurization measures since 2006. With continually increasing energy consumption and increasingly stringent environmental requirements, the production of FGD gypsum has exceeded 108 tons. The basic properties and the current beneficial applications of FGD gypsum are summarized here. The practical application of FGD gypsum in four fields-building materials, agriculture, material synthesis, and soil-and its impact on the environment, are analyzed. Finally, a new direction is proposed for the future utilization of FGD gypsum.

Pneumatic separation for crushed spent lithium-ion batteries.

Pneumatic separation was used to separate the valuable current collectors and harmful separators in spent lithium-ion batteries (LIBs) to avoid the plastic pollution caused by the separators in this study. Theoretical calculations for suspension velocities of the current collectors and separators indicate that they could be separated under special conditions. Furthermore, a special Z-shaped pneumatic separator was used to separate the current collectors and separators for the first time. Experiments for manually cut samples indicate that the efficiency of pneumatic separation is approximately 100% with the sizes and airflow velocities in the range of 3-4 cm and 6.96-7.8 m/s, respectively. Furthermore, industrial experiments of pneumatic separation indicate that the recoveries of the current collectors and separators are approximately 99.23% and 98.64%, respectively. Computer simulations of the separation process indicate that the turbulence and the changes in high-speed zones in the pneumatic separator benefit the separation of current collectors and separators. In conclusion, pneumatic separation is a promising technology to separate crushed current collectors and separators.

Thermal degradation behaviors and evolved products analysis of polyester paint and waste enameled wires during pyrolysis.

The thermal degradation behaviors and evolved products analysis of polyester paint and waste enameled wires during pyrolysis were studied. Thermogravimetric (TG) and differential thermogravimetric (DTG) analyses were performed to investigate the mass loss characteristics. The pyrolysis solid residues generated during the process under optimal condition were detailedly analyzed by Fourier-transform infrared spectroscopy (FTIR). Meanwhile, the pyrolysis gas and oil generated were analyzed by gas chromatography-mass spectrometry (GC-MS). Kinetic analysis adopted the Ozawa-Flynn-Wall (OFW) model to confirm the reaction series by the variation pattern of activation energy. The results indicated that the pyrolysis of polyester paint and waste polyester enameled wires can be divided into three stages. The average activation energy of polyester paint and waste polyester enameled wires pyrolysis was 323.34 kJ/mol and 215.95 kJ/mol, respectively. The optimized pyrolysis temperature for polyester paint and waste polyester enameled wires was 500 °C and 900 °C, respectively. The chemical compositions of the pyrolysis residues of polyester paint and waste polyester enameled wires were basically same, mainly containing the compounds with CH, CO, aromatic ring, methyl, and aromatics bonds. The pyrolysis gas of polyester paint was mainly composed of C2H6, while that of waste polyester enameled wires mainly consisted of C2H6 and C4H8O. The main components of the pyrolysis oil polyester paint and waste polyester enameled wires were basically same, mainly containing long chain hydrocarbons, long chain alkenes, alcohols, phenol, ketone, aldehyde, and aromatic.

Combined effects of jarosite and visible light on chalcopyrite dissolution mediated by Acidithiobacillus ferrooxidans.

Although jarosite and visible light are important factors for the formation of acid mine drainage (AMD), the effects of combined jarosite and visible light on chalcopyrite biodissolution have not been explored until now. In order to fill this knowledge gap, the combined effects of jarosite and visible light on chalcopyrite dissolution mediated by Acidithiobacillus ferrooxidans were investigated. The results indicated that jarosite and visible light could significantly accelerate chalcopyrite biodissolution, thus releasing more copper ions, iron ions and producing more acid. This in turn suggests enhanced generation of AMD under these conditions. Biodissolution results, mineral surface morphology, mineralogical phase and elemental composition analyses revealed that the promotion of chalcopyrite dissolution by additional jarosite and visible light was mainly attributed to the acceleration of ferric iron/ferrous iron cycling and the inhibition of the formation of a passivation layer (jarosite and Sn2-/S0) on the surface of chalcopyrite. This study provides a better understanding of the effects of jarosite and visible light on chalcopyrite biodissolution. In the future, the influences of jarosite and visible light on chalcopyrite dissolution should be considered in AMD evaluation to ensure reliability.

Pyrolysis and physical separation for the recovery of spent LiFePO4 batteries.

In this study, a novel process consisting of pyrolysis and physical separation was proposed to comprehensively recycle spent lithium ion batteries (LIBs). The discharge and pyrolysis behaviors of spent LIBs, the recovery of electrolyte from the spent LIBs by low-temperature volatilization, and the recovery of valuable materials from the pyrolytic residues through physical separation were studied in detail. The results indicated that approximately 99.91% of the organic electrolytes was recycled, and the lithium salt (LiPF6) in the batteries was disposed by pyrolysis process. The active materials could be effectively separated from current collectors after the pyrolysis under N2 at 550 °C for 2 h. The pyrolytic gas was mainly composed of light alkenes, and the pyrolytic tar was mainly composed of aromatic long chain alkenes and light alcohols. Pyrolytic residues were recycled by color sorting, high-pressure water cleaning and flotation processes, and about 99.34% of Al, 96.25% of Cu, and 49.67% of cathode active materials were recovered from the spent LIBs. Finally, electrochemical tests indicate that the cathode active materials obtained by the process can be used to produce new batteries.

Influence of Mixing and Nanosolids on the Formation of Nanobubbles.

The generation of nanobubbles (NBs) by replacing different dissolved gas solutions has been widely adopted. Recently, we have found that mixing solutions with different gas contents can also produce a large number of NBs. However, the mechanism of the formation of NBs during mixing has not been well explored. Here, we designed a series of experiments to investigate the influence of mixing of different solutions on the concentration and size contribution of formed NBs via the help of nanoparticle track analysis. The effect of nanosolids was also investigated. The pressurization and depressurization were used to produce NBs. The results indicated that NBs can be influenced by the gas contents and nanosolids. The addition of nanosolids is beneficial to produce more NBs. Both the nanosolids and gas contents together are expected to substantially increase the concentration of NBs. These results will be very helpful to understand the formation and stability of NBs.

Inhibition mechanism of Ca2+, Mg2+ and Fe3+ in fine cassiterite flotation using octanohydroxamic acid.

The existence of metal ions should not be ignored in both hydrometallurgy and flotation. In this study, the effects of Ca2+, Mg2+ and Fe3+ on the flotation performance of cassiterite using octanohydroxamic acid (OHA) as the collector were investigated by micro-flotation tests, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, contact angle, zeta (ζ) potential measurements and atomic force microscopy (AFM) imaging. The results of the flotation and contact angle experiments showed that the addition of Ca2+, Mg2+ and Fe3+ significantly decreased both the recovery and contact angle of cassiterite with pH ranged from 6.0 to 12.0 in the presence of OHA collector. ζ-Potential measurements, solution chemistry analysis and FTIR measurements indicated that the flotation recovery of the cassiterite declined due to the CaOH+, MgOH+ and Fe(OH)3 sites on the cassiterite surface. XPS results indicated that the chemisorption of OHA and calcium ions on the cassiterite surface finally changed its chemical properties. The AFM images also revealed that new species Fe(OH)3 of Fe3+ formed and adsorbed on the cassiterite surface at pH 9.0. The adsorption of Fe(OH)3 reduced the adsorption of OHA on the cassiterite surface, thus the hydrophobicity of cassiterite was deteriorated.

Sulfidation mechanism of ZnO roasted with pyrite.

Sulfidation is a widely used technology to improve the floatability of oxidized metal minerals or to stabilize the heavy metals in various wastes. The sulfidation mechanism of ZnO with pyrite was detailedly studied by thermodynamic calculation and roasting experiments. The sulfidation behaviors, phase transformations, microscopic morphology and surface properties were investigated by TG-DSC, ICP, XRD, SEM-EDS, and XPS analysis. The results indicate that the nature of the sulfidation is the reaction of ZnO with the gaseous sulfur generated by the decomposition of pyrite. Pyrite instead of sulfur as the sulfidizing agent can not only relieve the volatilization loss of sulfur but also enhance the formation of liquid phase and thus facilitate the growth of ZnS particles. The sulfidation reaction belongs to surface chemical reaction and relates to the migration of oxygen from the inside of ZnO to its surfaces. The presence of carbon not only eliminates the release of SO2, but also decreases the decomposition temperature of pyrite and promotes the sulfidation of ZnO. The addition of Na2CO3 promotes the sulfidation of ZnO at lower temperatures (below 850 °C) and enhances the growth of ZnS particles but has a negative effect on the sulfidation at higher temperatures.

The Role of Nanobubbles in the Precipitation and Recovery of Organic-Phosphine-Containing Beneficiation Wastewater.

Dissolved air flotation (DAF) is broadly applied in wastewater treatment, especially for the recovery of organic pollution with low concentration. However, the mechanism of interaction between nanoscale gas bubbles and nanoparticles in the process of DAF remains unclear. Here, we investigated the role of nanobubbles in the precipitation of styryl phosphoric acid (SPA)-Pb particles and recovering organic phosphine containined in beneficiation wastewater by UV-vis (ultraviolet-visible) spectra, microflotation tests, nanoparticle tracking analysis, dynamic light scattering, and atomic force microscopy measurements. As suggested from the results, nanobubbles can inhibit the crystallization of SPA-Pb precipitation, which makes the sediment flotation recovery below 20%. After the precipitation crystallization is completed, nanobubbles can flocculate precipitated particles, which can promote the flotation recovery of precipitated particles to 90%. On the basis of the results, we proposed a model to explain the different roles of nanobubbles in the process of precipitation and flotation of SPA-Pb particles. This study will be helpful to understand the interaction between nanobubbles and nanoparticles in the application of flotation.

Human cytomegalovirus triggers the assembly of AIM2 inflammasome in THP-1-derived macrophages.

Absent in melanoma 2 (AIM2) inflammasome is a multiprotein complex which plays a pivotal role in the host immune response to multiple pathogens. The role of AIM2 in human cytomegalovirus (HCMV) infection is poorly studied. Thus, using a small inference RNA (siRNA) approach and THP-1 derived macrophage cells infected with HCMV AD169 strain, we investigated the impact of HCMV infection on AIM2-mediated molecular events. Compared to wild-type cells, AIM2-defiecient macrophages showed a limited ability to activate caspase-1, process IL-1ß, and induce cell death. In addition, AIM2-defiecient cells were unable to efficiently control HCMV infection, as the transcription of virus DNA polymerase gene UL54 and major tegument protein gene UL83 were higher compared to wild-type cells. In conclusion, HCMV infection induces an AIM2 inflammasome response, which negatively influences viral life cycle.

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature.

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1-xFexS). The oxidation of synthetic Zn1-xFexS is easier than marmatite in air.

Hydrothermal Synthesis and Electrochemical Properties of Spherical α-MnO2 for Supercapacitors.

In the present work, spherical α-MnO2 with a high specific capacitance was synthesized by a two-step hydrothermal route. MnCO3 precursors were first prepared by a common hydrothermal method, and then converted to α-MnO2 via a hydrothermal reaction between the precursors and KMnO4 solutions. The effects of hydrothermal temperature on the morphology, crystal structure and specific area of the MnO2 were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and BET measurements. The electrochemical capacitive properties of the manganese dioxides with different morphologies and structures were evaluated by cyclic voltammetry and galvonostatic charge-discharge tests. The results showed that the temperature in the second hydrothermal step had prominent impact on the capacitive properties of a-MnO2. The MnO2 synthesized at 150 *C exhibited a highest specific capacitance of 328.4 Fx g(-1) at a charge-discharge current density of 100 mA x g(-1).

Effects of pyrite and bornite on bioleaching of two different types of chalcopyrite in the presence of Leptospirillum ferriphilum.

The effects of pyrite and bornite on bioleaching of two different chalcopyrite samples by Leptospirillum ferriphilum were studied for the first time. Results showed that bioleaching behaviors of the two chalcopyrite samples were extremely different. Bornite decreased the redox potential (ORP) and maintained it at an appropriate range (380-480 mV vs. Ag/AgCl) to promote chalcopyrite (A) dissolution, but caused the redox potential out of the optimum range and inhibited chalcopyrite (B) dissolution. Large amount of pyrite decreased the redox potential and maintained it at an optimum range to promote chalcopyrite (A) dissolution, while increased the redox potential and kept it at appropriate range for a longer period of time to enhance the dissolution rate of chalcopyrite (B). Chalcopyrite (B) had significantly higher values of conductivity and oxidation-reduction rate when compared with those of chalcopyrite (A). The work is potentially useful in interpreting the inconsistence of the researches of chalcopyrite hydrometallurgy.

Insights into the relation between adhesion force and chalcopyrite-bioleaching by Acidithiobacillus ferrooxidans.

This paper presents a study on the relation between bacterial adhesion force and bioleaching rate of chalcopyrite, which sheds light on the influence of interfacial interaction on bioleaching behavior. In our research, Acidithiobacillus ferrooxidans (A. ferrooxidans) were adapted to grow with FeSO4 · 7H2O, element sulfur or chalcopyrite. Then, surface properties of Acidithiobacillus ferrooxidans and chalcopyrite were analyzed by contact angle, zeta potential and Fourier transform infrared spectroscopy (FTIR). Adhesion force between bacteria and chalcopyrite was measured by atomic force microscopy (AFM). Attachment and bioleaching behaviors were also monitored. The results showed that A. ferrooxidans adapted with chalcopyrite exhibited the strongest adhesion force to chalcopyrite and the highest bioleaching rate. Culture adapted with sulfur bacteria took second place and FeSO4 · 7H2O-adapted bacteria were the lowest. Bioleaching rate and bacterial attachment capacity were positively related to bacterial adhesion force, which is affected by the nature of energy source. According to this work, the attachment of bacteria to chalcopyrite surface is one of the most important aspects that influence the bioleaching process of chalcopyrite.