Green separation and decomposition of crystalline silicon photovoltaic module's backsheet by using ethanol.

The treatment and recycling of discarded crystalline silicon photovoltaic modules (c-Si PV modules) has become a research focus, but few research have paid attention to the standardized treatment of c-Si PV module's fluorinated backsheet. Improper management of fluorinated backsheet can pose ecological and human health risks. Therefore, this study presents a novel method for processing the backsheet. The proposed approach entailed the utilization of ethanol (CH3CH2OH) to separate the backsheet from the PV module. Subsequently, the separated backsheet underwent decomposition using an alkaline ethanol (NaOH-CH3CH2OH) solution. Finally, the backsheet was recovered in the form of terephthalic acid (TPA) with a purity of 97.47 %. This recovered TPA can then serve as a valuable raw material for producing new backsheets, fostering a closed-loop material circulation. Experimental results demonstrate that immersing the PV module in a 75 % CH3CH2OH-H2O solution at a temperature of 343 K for 30 min achieved 100 % separation of the backsheet. Furthermore, subjecting the separated backsheet to a 60 min reaction in an NaOH-CH3CH2OH solution with a temperature of 343 K and a NaOH concentration of 1.0 mol/L achieved complete decomposition. The reaction mechanism was analyzed through characterization methods such as SEM/EDS, NMR, FTIR and XRD. This method is efficient, non-toxic organic reagent-free and environmentally friendly, so it holds significant potential for further development in the field of c-Si PV module recycling.

Recycling of valuable metals from spent lithium-ion batteries by self-supplied reductant roasting.

The massive spent lithium-ion batteries (LIBs) need to be recycled due to their increasing decommission in recent years. This paper aims to propose an effective process that uses self-supplied reductant roasting and acid leaching to recover Lithium, Nickle, Cobalt and Manganese from spent LIBs. In the absence of external carbon resources, the waste membrane from spent LIBs was used as the reductant in the self-supplied reductant roasting. A thermodynamic analysis was conducted to judge the possible reduction reaction between the cathode material and waste membrane. Then, the effects of roasting temperature, roasting time and membrane dosage on the crystal structure and phase transformation of roasting products were investigated and optimized. After the roasting process, the valence state of metals in the cathode material decreased and the structure became loose and porous. Moreover, the layer structure of the cathode material was transformed into groups of Li2CO3, Ni, Co, NiO, CoO and MnO. Further, the reduction effect of cathode powders under each roasting condition was verified under the same leaching conditions. After leaching for 30 min, the leaching efficiencies of Li, Ni, Co and Mn were over 99% under the optimum roasting conditions. Finally, economic assessments proved that the proposed process is profitable. The whole process demonstrates an effective and positive way for recycling spent LIBs and making full use of their waste membrane, which promotes resource recovery and environmental protection.

Study on the thermal reduction effect of organic components in spent ternary lithium battery cathode active materials.

To improve the adhesion between cathode materials and current collector, and increase the electronic conductivity among electroactive substances, a certain proportion of conductive agents (acetylene black) and agglomerant (PVDF) are usually added in the battery manufacturing process. However, these conductive agents have negative effects on the recovery of cathode materials by pyrolysis or calcination. Recognizing this issue, a method based on the concept of "treating spent with spent" was developed in this paper. Organic matters contained in cathode active materials functioned as the reduction reagents, which can reduce the valence state of transition metals, resulting in the breakdown of the strong chemical bond and the stable layered structure of cathode materials. In this study, the thermal reduction effect of different organic components on cathode active materials was analyzed respectively to evaluate the reduction function of each component. XRD, XPS and ICP-MS were used to compare and analyze changes of phase, element compound state and ion leaching efficiencies of different cathode materials before and after thermal reduction under different amounts of reducing agents. The results show that both PVDF and acetylene black reduced the high-valent metals to low-valent oxides or elemental substances, demonstrating their thermal reduction capabilities. Comparisons of the XRD, XPS analysis and ion leaching results of thermal reduced products suggest that acetylene black has a stronger thermal reduction ability than that of PVDF. The results also show that the reduction of the high nickel cathode material (NCM811) is easier than that of the low nickel cathode material (NCM111).

The effect of preparation time and aeration rate on the properties of bulk micro-nanobubble water using hydrodynamic cavitation.

Fundamental research on bulk micro-nanobubbles (BMNBs) has grown rapidly due to the demand for their industrial applications and potential role in interfacial sciences. This work focuses on examining properties of such bubbles, including the number, concentration, zeta potential, and surface tension in water. For this purpose, BMNBs were generated by the hydrodynamic cavitation (HC) mechanism. Distilled water and air in the experiments were the liquid and gas phases, respectively. The characterization of bulk microbubbles (BMBs) and bulk nanobubbles (BNBs) were performed through focused beam reflectance measurement (FBRM) and nanoparticle tracking analysis (NTA) techniques, respectively. Zeta potential and surface tension of aqueous solutions were measured at different time and aeration rates. The results showed that aeration rate and preparation time had an important role in the properties of BNBs (concentration, bubble size, and surface charge) and BMBs (number, and bubble size). The instability of BMBs led to the rapid changes in the dissolved oxygen (DO) content in the water. The number of BMBs decreased when preparation time and aeration rate increased, but their size remained constant. By enhancing the preparation time and aeration rate, the concentration of BNBs improved first and then reduced. Additionally, the surface tension of an aqueous solution containing BNBs was significantly lower than that of pure water.

Recycling of valuable metals from spent cathode material by organic pyrolysis combined with in-situ thermal reduction.

From the perspective of environmental protection and resource recovery, recycling of spent lithium-ion batteries is a meaningful process. In this study, the removal of organics, liberatioin of electrode material, and reduction of high valence transition metal, as the key points in recycling efficiency of valuable metals, have been firstly achieved simultaneously by low temperature heat treatment recycling process. Pyrolysis characteristics of organics, phase transition behavior of spent cathode material and the thermal reduction mechanism were evaluated in the meantime. Results demonstrate that organics can be removed and the liberation of electrode materials can be improved by pyrolysis. High-valence transition metals in cathode materials are synchronously reduced to CoO, NiO, MnO, Ni, and Co based on the reducing action of organics, aluminum foil and conductive additives. At the same time, Li element exists in the form of Li2CO3, LiF and aluminum-lithium compound that can be recycled by water-leaching in the water impact crushing process while transition metals can be recycled by acid leaching without reducing agents. 81.26% of Li can be recycled from water-leaching process while the comprehensive recovery rate of Ni, Co, Mn is 92.04%, 93.01%, 92.21%, respectively. This study may provide an environmentally-friendly recycling flowchart of spent lithium-ion batteries.

Hydrometallurgical enhanced liberation and recovery of anode material from spent lithium-ion batteries.

The efficient recycling of spent anode material (SAM) from spent lithium-ion batteries (LIBs) is generally critical in terms of electronic waste recyclingas well as increasing resource shortage and environmental problems. This research reported a novel and green method to recycle lithium, copper foil, and graphite from SAM by water leaching treatment. The results indicated that 100% of graphite was exfoliated from the anode material and 92.82% leaching efficiency of lithium was obtained under the optimal conditions of 80 °C, 60 g/L, 300 rpm, and 60 min, respectively. This finding revealed that the SAM got a full liberation characteristic due to the removal of binder, which produced an ideal leaching lithium efficiency rivaling the acids' performance. The mechanism of the liberation of SAM and lithium leaching is presented based on the analysis of results. The graphite was purified and recovered after water leaching treatment. Besides, lithium was recovered in the form of lithium carbonate (Li2CO3), and the copper foil was recovered in a sheet. This study endeavors to develop an economical and environmentally feasible plan to recycle graphite, copper, and lithium from SAM.

Recent advances in pretreating technology for recycling valuable metals from spent lithium-ion batteries.

In recent years, the amount of spent lithium-ion batteries (LIBs) increase sharply due to the promotion of new energy vehicles and the limited service life. Recycling of spent LIBs has attracted much attention because of the serious environmental pollution and high economic value. Although some established techniques have been presented in spent LIBs recycling process, but most of them focus on cathode material recycling due to its high economic value. Therefore, preparation of high purity cathode material by a proper pretreating technology is an important procedure. In this paper, the technologies used in the pretreating process of spent LIBs are summarized systematically from three main points of discharging procedure, liberation, and separation. The collaborative application of multi-technologies is the key to realize efficient pretreating process, which can lay the foundation for the subsequent metallurgical process. In addition, an alternative pretreating flowchart of spent LIBs is proposed based on the multi-process collaboration. Pretreating procedures in this process are mainly based on the physical property difference, and they include "Discharging-Shredding-Crushing-Sieving-Separation".

A critical review of current technologies for the liberation of electrode materials from foils in the recycling process of spent lithium-ion batteries.

Proper disposal of spent lithium-ion batteries is beneficial for the resource recycling and pollution elimination. Full liberation of electrode materials, including the liberation between electrode material and current collector (copper/aluminum foils) and the liberation among electrode material particles, is the pivotal precondition for improving the recovery efficiency of electrode materials. In this article, authors attempt to carry out a summary of current technologies used in the liberation of electrode materials derived from spent lithium-ion batteries. However, specialized studies about the liberation of electrode materials are insufficient at present. This research clearly shows that: (1) Organic binder must be removed so as to improve the liberation and metallurgy efficiency of electrode materials; (2) A collaboration of varied technologies is the necessary process to achieve high liberation efficiency between electrode materials and copper/aluminum foils; (3) Pyrolysis may be a recommended technology for removal of organic binder because part of pyrolysis products can be recovered. Finally, an alternative recycling flowchart of spent LIBs is proposed.

Organics removal combined with in situ thermal-reduction for enhancing the liberation and metallurgy efficiency of LiCoO2 derived from spent lithium-ion batteries.

Liberation and reduction of cathode material are the necessary procedures for improving the recycling efficiency of cathode material derived from spent lithium-ion batteries. In this research work, a pyrolysis technology was utilized to remove the organic binder and enhance liberation of electrode materials. At the same time, pyrolysis treatment can facilitate the thermal-reduction of Co3+ in LiCoO2 to Co2+ with surface organics, which lays a foundation for the subsequent reductant-free acid leaching. Results indicate that the crystal structure of pure LiCoO2 is not changed at a pyrolysis temperature of 600 °C, but LiCoO2 transforms to CoO, Li2CO3, LiF, and Li2O under the reduction action of HF, pyrolytic carbon, and additive carbon black. Water-impact crushing is synchronized with water-leaching to separate electrode materials from aluminum foil and recover Li element. Afterwards, reductant-free acid leaching technology can be utilized to recycle Li and Co from spent LiCoO2 batteries. Recovery efficiency of Li element in water-leaching process was up to 92.17% while the remaining 7.83% of Li and all Co elements were recovered during reductant-free acid leaching process. Based on the foundation analysis, the green chemical process for recovering valuable metals from spent lithium-ion batteries was proposed.

Indium tin oxide recycling from waste colour filter glass via thermal decomposition.

Thermal decomposition was used to enrich indium tin oxide (ITO) from waste colour filter glass. The colour layer was destroyed through oxidation, and the ITO layer was separated from the glass substrate. With the increase in the temperature and time of thermal decomposition, the yield of ITO concentrate decreased, but the ITO recovery and enrichment ratio increased. Furthermore, the ITO could be effectively enriched at 600 °C and 8 min, where the yield, recovery and enrichment ratio of ITO were 0.06 %, 98 % and 1669, respectively. The particle size distribution of the ITO concentrate was mainly distributed in 0.1-1.3 and 2.6-42.0 µm, with cumulative percentages of 4.33 % and 95.55 %, respectively. Moreover, the crystal structure of recycled ITO was not changed. Substantial poisonous and harmful mixed flue gas are produced during thermal decomposition. After condensation and adsorption by activated carbon, the emission of mixed flue gas could be effectively controlled to avoid serious pollution to the atmospheric environment.

Separation of the cathode materials from the Al foil in spent lithium-ion batteries by cryogenic grinding.

An environmentally friendly technology of cryogenic grinding for recovering cathode materials from spent lithium-ion batteries was has been investigated in this paper. Differential Scanning Calorimeter was used to test the glass transition temperature of the organic binder. Advanced analysis techniques, a microcomputer-controlled electronic universal material-testing machine, a low-temperature impact testing machine, scanning electron microscopy and high-resolution 3 Dimension-X-ray microscopy, were utilized to analyze the effect of low temperature on the mechanical properties and morphology of cathode. Results show that the yield strength, tensile strength and impact strength of the current collector is significantly increased at low temperature, that the glass transition temperature of the organic binder is approximately 235 K. Low temperature enhances the strength of the current collector and causes the organic binder to fail. Therefore, cryogenic grinding could realize the selective grinding of the cathode and significantly improve the peel-off of the electrode materials. The peel-off efficiency of cathode materials was improved from 25.03% to 87.29% at the optimum conditions of low temperature pretreatment for 5 min and cryogenic grinding for 30 s. The experiments demonstrate that the cryogenic grinding can obviously facilitate the efficient recovery of cathode materials, revealing a great application prospective for the recycling of spent lithium-ion batteries.

Enhancement in leaching process of lithium and cobalt from spent lithium-ion batteries using benzenesulfonic acid system.

Recycling of valuable metals from spent lithium ion batteries (LIBs) is of great significance considering the conservation of metal resources and the alleviation of potential hazardous effects on environment. Thus, the present work focuses on enhancing the efficiency of leaching process for the recovery of cobalt and lithium from the cathode active materials of spent LIBs. In this study, benzenesulfonic acid (C6H5SO3H) with a reducing agent hydrogen peroxide (H2O2) was innovatively used as leaching reagents, and the operating variables were optimized to obtain higher leaching efficiencies. Results show the optimized leaching recovery of 99.58% Li and 96.53% Co was obtained under the conditions of 0.75 M benzenesulfonic acid, 3 vol% H2O2, a solid to liquid (S/L) ratio of 15 g/L, 500 rpm stirring speed, and 80 min leaching time at 90 °C. Moreover, a new kinetic model was introduced to describe the leaching kinetics of LiCoO2 from the cathode material. The apparent activation energies Ea for leaching of lithium and cobalt are 41.06 and 35.21 kJ/mol, respectively, indicating that the surface chemical reaction is the rate-controlling step during this leaching process. Further, the proposed recovery mechanism for spent cathode material was raised by analyzing the experimental results and characterizing the morphological and chemical state (i.e. SEM-EDS, XPS and XRD) of raw material and leaching residues. In comparison with the previous leaching process, this research was found to be efficient, low energy consumption, and environmental friendly.

A mathematical model to characterize the degree of coalification based on the low-angle region of the X-ray diffractogram.

Based on X-ray diffraction (XRD) pattern of coal, an empirical model for judging the coalification degree is used to calculate the ratio of the 002 peak height to the Full width at half maximum (FWHM). However, the existing models are often simpler and more suitable for judgment of the medium and low rank coal, while are not feasible in determination of high rank coal. In order to address this issue, the objective of this study is to establish a new modified mathematical model based on optimization of the existing empirical models. Through the calculation of Bragg equation, it demonstrates that the low-angle region (2θ= 3-10°) in the XRD pattern reflects the information of micropore in coal with a diameter of (0.884-2.94) nm. Accordingly, its diffraction intensity corresponds to the porosity rate in coal. As a result, the modified mathematical model has been established for characterizing the coalification degree by introducing the variation of porosity rate with the coal ranks creatively. The synergistic effects of the change regulation of organic matter peak and the porosity rate with coal rank ensure the accuracy of the model. Furthermore, the good stability and high reliability of new model are verified through the recalculation of a total of 14 coal samples. Study results demonstrated that the new method enabled to determine coal rank more conveniently and accurately in the industrial production.

Separation Process of Fine Coals by Ultrasonic Vibration Gas-Solid Fluidized Bed.

Ultrasonic vibration gas-solid fluidized bed was proposed and introduced to separate fine coals (0.5-0.125 mm fraction). Several technological methods such as XRF, XRD, XPS, and EPMA were used to study the composition of heavy products to evaluate the separation effect. Results show that the ultrasonic vibration force field strengthens the particle separation process based on density when the vibration frequency is 35 kHz and the fluidization number is 1.8. The ash difference between the light and heavy products and the recovery of combustible material obtain the maximum values of 47.30% and 89.59%, respectively. The sulfur content of the heavy product reaches the maximum value of 6.78%. Chemical state analysis of sulfur shows that organic sulfur (-C-S-), sulfate-sulfur (-SO4), and pyrite-sulfur (-S2) are confirmed in the original coal and heavy product. Organic sulfur (-C-S-) is mainly concentrated in the light product, and pyrite-sulfur (-S2) is significantly enriched in the heavy product. The element composition, phase composition, backscatter imagery, and surface distribution of elements for heavy product show concentration of high-density minerals including pyrite, quartz, and kaolinite. Some harmful elements such as F, Pb, and As are also concentrated in the heavy product.

Recovery of valuable components from waste LCD panel through a dry physical method.

A waste liquid crystal display (LCD) panel was recycled synthetically and cleanly by using dry physical methods, namely, mechanical exfoliation, dry crushing and vibrated gas-solid fluidized bed separation. Results of elemental and phase analyses show that indium and tin contents were enriched greatly in indium tin oxide concentrate obtained from colour filter and thin-film transistor glass. The results of crushing, ash content and scanning electron microscopic analyses show that when the LCD panel was crushed into particles smaller than 0.25mm, the polarizer film is nearly completely liberated from the glass. Moreover, the results of vibrated gas-solid fluidized bed separation show that gas velocity and separation time are the main factors influencing the separation. The vibration intensity of 6.8, gas velocity of 13.6cm/s and fluidizing time of 30s are the optimum operating parameters, and the degree of separation and recovery of polarizing film reached up to 37.69 and 72.3%, respectively. Based on these results, the combination of dry enrichment, dry crushing and dry separation in a flowsheet is proposed for recycling of waste LCD panel.

New technology for recovering residual metals from nonmetallic fractions of waste printed circuit boards.

Recycling of waste printed circuit boards is important for environmental protection and sustainable resource utilization. Corona electrostatic separation has been widely used to recycle metals from waste printed circuit boards, but it has poor separation efficiency for finer sized fractions. In this study, a new process of vibrated gas-solid fluidized bed was used to recycle residual metals from nonmetallic fractions, which were treated using the corona electrostatic separation technology. The effects of three main parameters, i.e., vibration frequency, superficial air flow velocity, and fluidizing time on gravity segregation, were investigated using a vibrating gas-solid fluidized bed. Each size fraction had its own optimum parameters. Corresponding to their optimal segregation performance, the products from each experiment were analyzed using an X-ray fluorescence (XRF) and a scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS). From the results, it can be seen that the metal recoveries of -1+0.5mm, -0.5+0.25mm, and -0.25mm size fractions were 86.39%, 82.22% and 76.63%, respectively. After separation, each metal content in the -1+0.5 or -0.5+0.25mm size fraction reduced to 1% or less, while the Fe and Cu contents are up to 2.57% and 1.50%, respectively, in the -0.25mm size fraction. Images of the nonmetallic fractions with a size of -0.25mm indicated that a considerable amount of clavate glass fibers existed in these nonmetallic fractions, which may explain why fine particles had the poorest segregation performance.

Triboelectric separation technology for removing inorganics from non-metallic fraction of waste printed circuit boards: Influence of size fraction and process optimization.

Removing inorganics from non-metallic fraction (NMF) of waste printed circuit boards (WPCBs) is an effective mean to improve its usability. The effect of size fraction on the triboelectric separation of NMF of WPCBs was investigated in a lab triboelectric separation system and the separation process was optimized in this paper. The elements distribution in raw NMF collected from typical WPCBs recycling plant and each size fraction obtained by sieving were analyzed by X-ray fluorescence (XRF). The results show that the main inorganic elements in NMF are P, Ba, Mn, Sb, Ti, Pb, Zn, Sn, Mg, Fe, Ca, Cu, Al and Si. The inorganic content of each size fraction increased with the size decreasing. The metal elements are mainly distributed in -0.2mm size fraction, and concentrated in middle product of triboelectric separation. The loss on ignition (LOI) of positive product and negative product is higher than that of the middle product for the -0.355mm size fraction, while the LOI presents gradually increasing trend from negative to positive plate for the +0.355mm size fraction. Based on the separation results and mineralogical characterizations of each size fraction of NMF, the pretreatment process including several mineral processing operations was added before triboelectric separation and better separation result was obtained.

Removing inorganics from nonmetal fraction of waste printed circuit boards by triboelectric separation.

Metals recycling from WPCBs has been studied for a long time, which results in the appearance of many proven techniques. However, the nonmetal fraction in WPCBs has not been fully recycled due to hybridpropertiesof inorganic and organic composition. In order to improve the usability of the nonmetal fraction from WPCBs, nonmetal materials separation by using a laboratory triboelectric separation system was carried out to improve the reuse efficiency of WPCBs nonmetal fraction. The optimum tribocharger material was investigated by using the charge-mass ratio measurement system, and PMMA is the optimum tribocharger material compared with PVC, PPFT, PPR, SS. The effects of airflow, voltage and feed rate on triboelectric separation were investigated. The product LOI of positive plate is up to 77.26% with recovery rate of 25.49%, while the product LOI of negative plate is down to 47.35% with recovery rate of 35.37%, and the remove rate of inorganics is up to 43.02% by triboelectric separation. The analysis results of X-ray diffraction indicate that the main inorganic materials mixed in nonmetal fraction are SiO2, Al2O3, CaO, Cu, Fe, Sn. The X-ray fluorescence analysis shows that the triboelectric separation can effectively remove the content of SiO2 and Al2O3. The scanning electron microscope images show that inorganics tribocharge positively and distribute in product collection grooves that close to negative plate.

Chemical and process mineralogical characterizations of spent lithium-ion batteries: an approach by multi-analytical techniques.

Mineral processing operation is a critical step in any recycling process to realize liberation, separation and concentration of the target parts. Developing effective recycling methods to recover all the valuable parts from spent lithium-ion batteries is in great necessity. The aim of this study is to carefully undertake chemical and process mineralogical characterizations of spent lithium-ion batteries by coupling several analytical techniques to provide basic information for the researches on effective mechanical crushing and separation methods in recycling process. The results show that the grade of Co, Cu and Al is fairly high in spent lithium ion batteries and up to 17.62 wt.%, 7.17 wt.% and 21.60 wt.%. Spent lithium-ion batteries have good selective crushing property, the crushed products could be divided into three parts, they are Al-enriched fraction (+2 mm), Cu and Al-enriched fraction (-2+0.25 mm) and Co and graphite-enriched fraction (-0.25 mm). The mineral phase and chemical state analysis reveal the electrode materials recovered from -0.25 mm size fraction keep the original crystal forms and chemical states in lithium-ion batteries, but the surface of the powders has been coated by a certain kind of hydrocarbon. Based on these results a flowsheet to recycle spent LiBs is proposed.