Spent Lead Acid Batteries Research Articles

PbS Quantum Dot Image Sensors Derived from Spent Lead-Acid Batteries Via an Environmentally Friendly Route

PbS Quantum Dot Image Sensors Derived from Spent Lead-Acid Batteries Via an Environmentally Friendly Route

Ultrasonic-Assisted Synthesis of Lead Citrate as Precursor for Preparation of Lead Oxide from Lead Sulfate

ABSTRACT In this study, an efficient method of lead recovery from lead sulfate in spent lead-acid batteries assisted by ultrasonic is developed using the citric acid–sodium citrate solution. Ultrasonic-assisted technology is employed to enhance the kinetics of lead sulfate leaching. Initially, the predominance area of the lead citrate complexes was analyzed. The study was conducted to evaluate the effect of ultrasonic-assisted technology on the kinetic behavior of lead sulfate within the citric acid–sodium citrate solution, thereby unveiling the differences between ultrasonic-assisted leaching and the non-ultrasonic-assisted leaching. Kinetic study indicated that the employment of ultrasonic-assisted technology could effectively reduce the apparent activation energy during the desulfurization process, decreasing the energy initially required from 43.27 kJ/mol to 35.15 kJ/mol. Furthermore, the ultrasonic-assisted leaching led to successful preparation of lead citrate precursor, characterized by a smaller particle size and larger specific surface area. Systematic investigations were performed on the thermal decomposition process of these precursors and the effects of calcination temperature and holding time on the properties of calcination products. It was revealed that pure porous lead oxide powder with a purity of 99.9% could be produced successfully under the conditions of calcination temperature at 350°C and holding time of 1 h. The research provides an innovative process for the efficient recovery of lead from spent lead acid batteries.

Batch Production of Lead Sulfate from Spent Lead–Acid Batteries via an Oxygen-Free Roasting Route: A Negative-Carbon Strategy

Multicomponent lead compounds, including lead (Pb), lead oxide (PbO), lead dioxide (PbO2), and lead sulfate (PbSO4), in spent lead–acid batteries (LABs), if not properly disposed of and recycled, will cause serious pollution and damage to the ecological environment. Pyrometallurgical smelting performed above 1000 °C often incurs high energy consumption and lead pollution. In this study, a low-temperature (300 °C), oxygen-free roasting process was proposed. With potassium bisulfate (KHSO4) as the roasting reagent, the uniform conversion of multicomponent lead compounds from spent lead paste (SLP) to PbSO4 was successfully realized in one step. We observed that PbO2 species were relatively chemically stable, during the oxygen-free roasting. However, the decomposition of PbO2 into PbO can be achieved by heating to 300 °C, resulting in an effective conversion to PbSO4. The optimal conditions for PbSO4 production were a heating temperature of 300 °C, an SLP/KHSO4 mass ratio of 1:1, and a holding time of 10.0 min. Life cycle assessment results show that the recycling of 1.0 t spent LABs can reduce carbon emissions of 2.45 t CO2 and smog of 0.13 t. Our research provides an emission-free, low-temperature, and negative-carbon strategy for facile and cost-effective recycling of spent LABs, as an alternative to traditional pyrometallurgical smelting.

Predicting the cost of a 24 V soluble lead flow battery optimised for PV applications

Providing reliable electricity from small-scale renewable power is an important challenge for emerging economies. The soluble lead flow battery (SLFB) is a promising battery for this application, as it has a simple architecture making it relatively robust, and a lifetime of 2000 cycles demonstrated at the cell level. Also, the electrolyte is manufacturable directly from spent lead acid batteries. There is a need for techno-economic models to allow the cost/performance of a complete system to be defined and optimised.Such a model is defined here for the first time and used in a multi-objective optimisation to design a 24 V system for a charging hub in Sierra Leone. A 4 h duration was found to be optimal, and electrolyte for a 3.5 kW/14 kWh system would fit in a 1000 L IBC.Methanesulfonic acid was found to be the largest cost component of the 4 h system, with graphitic bipolar plates next. Both have low raw material costs, and in an optimistic scenario a total component cost of <£50/kWh would be achieved, half that of current NMC Li-ion cells. The greatest technical risk to achieving low cost is deposit thickness of lead dioxide. This important research gap should be addressed.

Natrium Diacid Phosphate-Manganese-Lead Vitroceramics Obtained from Spent Electrodes

NaH2PO4-MnO2-PbO2-Pb vitroceramics were studied usinginfrared (IR), ultraviolet-visible (UV-Vis) and electron paramagnetic resonance (EPR) spectroscopies to understand the structural modifications as potential candidates for electrode materials. The electrochemical performances of the NaH2PO4-MnO2-PbO2-Pb materials were investigated through measurements of cyclic voltammetry. Analysis of the results indicates that doping with a suitable content of MnO2 and NaH2PO4 removes hydrogen evolution reactions and produces a partial desulphatization of the anodic and cathodic plates of the spent lead acid battery.

Progress in Waste Lead Paste Recycling Technology from Spent Lead–Acid Battery in China

Progress in Waste Lead Paste Recycling Technology from Spent Lead–Acid Battery in China

Recycling of Lead Pastes from Spent Lead–Acid Batteries: Thermodynamic Constraints for Desulphurization

Lead–acid batteries are important to modern society because of their wide usage and low cost. The primary source for production of new lead–acid batteries is from recycling spent lead–acid batteries. In spent lead–acid batteries, lead is primarily present as lead pastes. In lead pastes, the dominant component is lead sulfate (PbSO4, mineral name anglesite) and lead oxide sulfate (PbO•PbSO4, mineral name lanarkite), which accounts for more than 60% of lead pastes. In the recycling process for lead–acid batteries, the desulphurization of lead sulfate is the key part to the overall process. In this work, the thermodynamic constraints for desulphurization via the hydrometallurgical route for recycling lead pastes are presented. The thermodynamic constraints are established according to the thermodynamic model that is applicable and important to recycling of lead pastes via hydrometallurgical routes in high ionic strength solutions that are expected to be in industrial processes. The thermodynamic database is based on the Pitzer equations for calculations of activity coefficients of aqueous species. The desulphurization of lead sulfates represented by PbSO4 can be achieved through the following routes. (1) conversion to lead oxalate in oxalate-bearing solutions; (2) conversion to lead monoxide in alkaline solutions; and (3) conversion to lead carbonate in carbonate solutions. Among the above three routes, the conversion to lead oxalate is environmentally friendly and has a strong thermodynamic driving force. Oxalate-bearing solutions such as oxalic acid and potassium oxalate solutions will provide high activities of oxalate that are many orders of magnitude higher than those required for conversion of anglesite or lanarkite to lead oxalate, in accordance with the thermodynamic model established for the oxalate system. An additional advantage of the oxalate conversion route is that no additional reductant is needed to reduce lead dioxide to lead oxide or lead sulfate, as there is a strong thermodynamic force to convert lead dioxide directly to lead oxalate. As lanarkite is an important sulfate-bearing phase in lead pastes, this study evaluates the solubility constant for lanarkite regarding the following reaction, based on the solubility data, PbO•PbSO4 + 2H+ ⇌ 2Pb2+ + SO42− + H2O(l).

Recycling spent lead acid batteries into aqueous zinc-ion battery material with ultra-flat voltage platforms

The harmless disposal of lead paste in the spent lead-acid batteries (LABs) remains an enormous challenge in traditional pyrometallurgical recycling. Here, we introduced a hydrometallurgical method for the recycling of the spent LABs’ waste to obtain the β-PbO as a novel zinc ion batteries (ZIBs) active material. The obtained β-PbO exhibits ultra-flat charge/discharge voltage platforms (0.21 mV/(mAh g−1)) and stable specific capacity. During the charge/discharge, the β-PbO spontaneously triggers the formation of (ZnSO4)[Zn(OH)2]3·5H2O (ZHS) micro-sheets as a surface passivation layer. Moreover, the ex-situ X-ray spectra reveal that the reversible phase transformation occurs between PbSO4 and Pb with the assistance of ZHS by adjusting the PH value on the electrode-electrolyte interface. The synergistic two-phase-reaction mechanism generates ultra-flat voltage platforms upon the charge/discharge. This “energy-saving and environment-friendly” recycling route eliminates the major source of emission of pollution particulates/gases compared to the traditional pyrometallurgical recycling, while at the same time replacing energy-consuming and environmentally detrimental processes of synthesis of current ZIBs cathodes.

Pb-MOF electrosynthesis based on recycling of lead-acid battery electrodes for hydrogen sulfide colorimetric detection

Spent lead-acid batteries are environment emerging contaminants and very harmful to health. In this work, we developed one-pot electrochemical method of recycling lead electrodes for the preparation of Pb metal–organic framework, using 1,3,5-benzenetricarboxylic acid as organic ligand (Pb(btc)-1). In H2S solution, a color change can be observed on the Pb(btc)-1 surface, which is caused by PbS formation and, therefore, it was studied as a smart compound for H2S quantification. Colorimetric techniques, as diffuse reflectance and digital image (DI) analysis obtained on a smartphone, were used for H2S quantification. The grayscale and RGB color histograms were obtained from the recorded images and treated by partial least squares (PLS) regression method directly on a smartphone, or using the MATLAB® software. The colorimetric techniques showed greater sensitivity, resulting in a limit of detection of 0.11 mmol.L-1, which is slightly lower than the DI using MATLAB® software (0.21 mmol.L-1). The accuracies of the colorimetric techniques were similar and present feasible values when compared to Horwitz criteria. Thus, the H2S sensor ends the lead-acid battery recycling cycle, giving a colorimetric device by a low energy processing of the lead electrode.

A novel approach to recover lead oxide from spent lead acid batteries by desulfurization and crystallization in sodium hydroxide solution after sulfation

With the increasing demand for lead acid batteries, there were a great number of spent lead acid batteries generated. They have the dual characteristics of resource and harm, making the recovery an important subject. In this paper, a novel approach to recover lead oxide from spent lead acid batteries by desulfurization and crystallization in sodium hydroxide solution after sulfation was proposed. During sulfation process, 85% sulfuric acid (17.786 g sulfuric acid per 2 g negative pastes) was the best for negative lead pastes, and the content of lead sulfate was up to 91.34%. For positive lead pastes, the optimal conditions were 85% sulfuric acid (17.786 g sulfuric acid per 2 g positive pastes) at 65 °C, and the content of lead sulfate was 95.69%. In the process of desulfurization and crystallization, the optimal parameters for the recovery ratio of lead oxide were 90 mg/L of solid-liquid ratio, 42 mL of mother liquor retention, and 8.24 mol/L of sodium hydroxide concentration. The recovery ratio and purity of lead oxide were 95.72% and 95.31% under the optimal conditions. Compared to pyrometallurgy and traditional hydrometallurgy, this novel approach greatly shortens the process flow. It reduces the energy consumption and secondary pollution, having great potential for industrial application.

Vacuum decomposition thermodynamics and experiments of recycled lead carbonate from waste lead acid battery

Lead acid batteries have been widely used in different fields, so abundant waste lead acid battery was generated. Waste lead acid battery is regarded as a toxic material due to the metallic lead and the lead paste compounds. Once lead and its compounds enter the human body and the environment, which will cause serious threats. At present, the waste lead acid batteries are mainly recovered in the form of metal lead, which has many problems. Thus, this paper put forward a novel technology to recycle waste lead acid battery. Vacuum thermal decomposition was employed to treat recycled lead carbonate from waste lead acid battery. Thermodynamics analysis and experiments were finished from the reaction free energy of lead carbonate decom-position and vacuum furnace. The results showed that the recycled lead carbonate began to be decomposed when the temperature reached 250?C. Above 340?C, most of intermediate PbCO3?2PbO were converted to red ?-PbO and then transformed to yellow ?-PbO when the temperature was raised further to 460?C. Furthermore, the study provided the fundamental data for the preparation of ?-PbO and ?-PbO in vacuum, which also demonstrated a new way for the reuse of spent lead acid battery resource and an outlook of sustainable production.

Electrochemical behavior and electrolytic preparation of lead in eutectic NaCl−KCl melts

Abstract A novel molten salt extraction process consisting of chlorination roasting and molten salt electrolysis was proposed to develop a more efficient and environmental friendly technology for recovering lead from spent lead acid batteries (LABs). The feasibility of this process was firstly assessed based on thermodynamics fundamentals. The electrochemical behavior of Pb(II) on a tungsten electrode in the eutectic NaCl−KCl melts at 700 °C was then investigated in detail by transient electrochemical techniques. The results indicated that the reduction reaction of Pb(II) in NaCl−KCl melts was a one-step process exchanging two electrons, and it was determined to be a quasi-reversible diffusion-controlled process. Finally, potentiostatic electrolysis was carried out at −0.6 V (vs Ag/AgCl) in the NaCl−KCl−PbCl2 melts, and the obtained cathodic product was identified as pure Pb by X-ray diffraction analysis. This investigation demonstrated that it is practically feasible to produce pure Pb metal by electrochemical reduction of PbCl2 in eutectic NaCl−KCl melts, and has provided important fundamental for the further study on lead recovery from spent LABs via molten salt extraction process.

A green and cost-effective process for recovery of high purity α-PbO from spent lead acid batteries

Herein, we propose a green, cost-effective and short-loop route for recovering high-purity α-lead oxide (α-PbO) from spent lead-acid batteries. This newly proposed route consists of leaching, carbonation and thermal decomposition processes. In the leaching process, the lead sulfate (PbSO4) from spend lead paste was reacted with conjugated solution of ammonium sulfate-ammonia ((NH4)2SO4–NH3) to form a soluble complex. The dissolved PbSO4 in the conjugated solution was converted into lead carbonate (PbCO3) precipitate via absorption of carbon dioxide (CO2). Afterwards, the high-purity α-PbO was obtained by thermal decomposition of PbCO3. Results show that the leaching rate of PbSO4 from lead paste reaches up to 99.8 ± 0.15%, the recovery rate of lead is 99.85% and the purity of the obtained α-PbO is as high as 99.992%, indicating the recovered α-PbO has high purity. As well, the recovered α-PbO shows a better electrochemical activity than the conventional Shimadzu ball-milling method. Beside of recovering high-purity α-PbO, the used raw materials of conjugated solution and the intermediate product of CO2 could be collected and utilized in the next batch. Therefore, the present work develops a new green and economic route to solve the recovery problems of high purity α-PbO from spent lead-acid batteries.

Recycling of mixed lithium-ion battery cathode materials with spent lead-acid battery electrolyte with the assistance of thermodynamic simulations

Based on the concept of recycling waste with waste, the mixed cathode materials of spent lithium-ion batteries were recycled with waste electrolyte from spent lead–acid batteries. With the assistance of thermodynamic simulations, the optimized recycling path of the mixed cathode materials was proposed and tested. A higher overall recycling ratio of valuable metals, that is, 94.9% of lithium, 94.5% of cobalt, 94.4% of nickel, and 95.5% of manganese, was achieved by replacing the oxalates/carbonates used in the precipitation process with sulfides and reducing the solubility of lithium carbonate in the lithium precipitation step at room temperature with ethanol. A higher ethanol-to-water ratio yielded a higher precipitation ratio of lithium until the ratio reached 5:1. High-purity lithium carbonate and cobalt (99.9%) were recovered as nanoparticles and nanoribbons, respectively, through precipitation using carbon dioxide in a solution with a 4:1 ethanol-to-water ratio and electrodeposition at E = −0.4 V in a traditional three-electrode system. Furthermore, the poisonous heavy metal (lead) was separated and stabilized as lead sulfide.

From Lead Paste to High-Value Nanolead Sulfide Products: A New Application of Mechanochemistry in the Recycling of Spent Lead–Acid Batteries

The recycling of lead in spent lead–acid batteries (LABs) is an effective measure to cope with the depletion of primary lead ore. In this study, multicomponent lead in the lead paste of spent LABs ...

Current trends and future perspectives in the recycling of spent lead acid batteries in India

Lead is used in construction, military applications, and in various alloys but mainly in producing Lead Acid Batteries (LABs). The emerging automobile sector, electric vehicle industries, solar power systems and telecommunication industries require more and more lead acid battery due to their excessive growth. Therefore, lead acid batteries are in ever increasing demand in various sectors and in return its scrap also increasing day by day. One of the best qualities of lead acid batteries is that these are almost completely recyclable and the lead metal can also be extracted out in largest percentage in recovery. Out of total lead usage 80% of lead is used in LABs. Maximum 100% lead can be recycled and recovered from the lead acid battery.The benefits of using secondary i.e. recycled lead are less CO2 emission (up to 99%) and another is employment to approx 6–7 lakh people (In India) in recycling industry. This stature can further be increased if supported by strong legislation. The problems in India in recycling sector are that lack of formal planned recycling industry in India. The industry is not considered as a respected one and lack of particular zones for recycling.Various new techniques like pyrometllurgy, hydrometallurgy and green technologies can be used for recycling in India apart from the traditional ones. Most of them are accomplished but need to be explored more.

Emergy based sustainability evaluation of spent lead acid batteries recycling

Sustainability evaluation of lead acid batteries recycling enables quantitative analyses of the true value of resources, the environment and economy of the processes thus to provides recommendations to improve process sustainability. However, the environmental impacts of pollutants haven’t been considered in the emergy-based sustainability assessment indicators. To this end, an improved emergy analysis method is proposed to evaluate the efficiency and sustainability of the lead acid batteries recovery process system. Firstly, the ecological effects of pollutant emissions are converted to equivalent waste emergy using dilution, eco-indicator 99 and the land erosion methods. Then, the waste emergy and product emergy are included in the emergy index system to provide improved emergy indices. In addition, in order to assess the system’s resource recovery rate and clean production level, technical efficiency and environmental have been included into the performance indicators. Finally, according to the evaluation results of emergy indicators, improvement measures for the optimisation system can be improved. To verify the feasibility of the proposed method, the sustainability evaluation of the production process of the lead acid batteries recycling system (including disassembly, classification and various separation materials processing processes) is conducted, and the results show that pollutant emissions reduce the effectiveness and sustainability of the system. This method reflects the overall performance of the system, compared with the traditional emergy method. The proposed method can be utilized as an effective tool for sustainability evaluation and optimisation of lead acid batteries recovery process system.

Lead recovery from spent lead acid battery paste by hydrometallurgical conversion and thermal degradation.

Spent lead paste is the main component in lead-acid batteries reaching end of life. It contains about 55% lead sulphate and 35% lead dioxide, as well as minor amounts of lead oxide. It is necessary to recycle spent lead paste with minimal pollution and low energy consumption instead of the conventional smelting method. In this study, a novel approach involving hydrometallurgical desulphurisation and thermal degradation is developed to recover lead as PbO products from spent lead acid batteries. First, the desulphurisation effects and phase compositions of products with different transforming agents were compared, and the optimum conditions using (NH4)2CO3 as a transforming agent were determined. And then, the thermal degradation processes of both precursors lead carbonate and lead dioxide were investigated to prepare α-PbO, Pb3O4, and β-PbO products in argon and air atmospheres, respectively. Both the desulphurisation precursors and the calcination products were characterised by thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy. The results showed that the lead oxide products were prepared, including α-PbO at 450°C in argon, Pb3O4 and β-PbO at 480°C and 620°C in air, respectively.

Spent Lead–Acid Battery Recycling by Hydraulic Fluidized Bed Sorting

Abstract Spent lead–acid batteries (LABs) have been extensively studied because of their environmental pollution, public health harmfulness, and their use as raw materials for the production of rec...

Sustainable Treatment for Sulfate and Lead Removal from Battery Wastewater

In this study, we present a low-cost and simple method to treat spent lead–acid battery wastewater using quicklime and slaked lime. The sulfate and lead were successfully removed using the precipitation method. The structure of quicklime, slaked lime, and resultant residues were measured by X-ray diffraction. The obtained results show that the sulfate removal efficiencies were more than 97% for both quicklime and slaked lime and the lead removal efficiencies were 49% for quicklime and 53% for slaked lime in a non-carbonation process. After the carbonation step, the sulfate removal efficiencies were slightly decreased but the lead removal efficiencies were 68.4% for quicklime and 69.3% for slaked lime which were significantly increased compared with the non-carbonation process. This result suggested that quicklime, slaked lime, and carbon dioxide can be a potential candidate for the removal of sulfate and lead from industrial wastewater treatment.