Spent Lead Acid Batteries Research Articles

Tracking flows of secondary vehicle batteries in China

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.

Synthesis of the PbS Dendritic Nanostructure Recovered from a Spent Lead-Acid Battery via an Integrated Vacuum Chlorinating and Hydrothermal Process

An integrated two-step process, comprising vacuum chlorinating and hydrothermal synthesis, is developed for direct recovery of the three-dimensional lead sulfide (PbS) dendrite product from the lea...

Identification of management strategies and generation factors for spent lead acid battery recovery plant wastes in Turkey.

The recovery of spent or waste lead acid batteries is important both for the management of lead input to the environment and to meet the lead demand of the market in a more energy and cost effective manner than primary production. As an important producer of lead acid batteries for the Middle Eastern and Eastern European market, Turkey seems to meet 22%-52% of its total lead demand by waste lead acid battery recovery. In this study, the wastes from Turkish waste lead acid battery recovery plants are identified and management strategies that are both technically sufficient and economically feasible for each of these wastes are complied. Furthermore, ranges of the amount of each waste generated per mass of final lead produced in these plants are estimated. Some of the most significantly generated wastes are lead containing dusts, wash water treatment sludges and slags from smelting furnaces with generation rates between 5-250, 1-150 and 5-100 kg t-1 of product lead, respectively. Many of these can be fed back to the recovery process inside the plants except a subset of slags that are called 'final slag' and have low (5%-6%) lead content. Final slags can either be recovered for the production of cement, road-filling materials or abrasives proven that they are in a non-leachable, stable state or should be stored at hazardous waste landfills. For improved environmental performance, newly emerging techniques that eliminate the generation of such slags are also discussed and suggested.

Sustainability evaluation of secondary lead production from spent lead acid batteries recycling

In China, rapid development of electric vehicles resulted in large consumption of lead and lead products such as lead acid batteries (LABs). Recycling LABs is one option to mitigate natural resource depletion and corresponding environmental issues. However, few studies have been conducted to measure the operation of LABs recycling industry. Consequently, it is necessary to initiate such a study so that key barriers on promoting this industry can be identified. Under such a circumstance, this study proposes an emergy-based evaluation framework to evaluate one LABs recycling firm in Yunnan so that the emissions’ impact on human health and ecosystem from this firm can be quantified. A set of emergy-based indicators are established to evaluate the sustainability of this recycling firm. The results show that the investigated system had a higher emergy efficiency compared with that primary ore exploitation system. However, the extremely low values of emergy indicators indicate that this recycling system could not achieve sustainable development goals due to its heavy dependence on nonrenewable resources. Based upon such results and local realities, policy suggestions are raised in order to improve the overall sustainability of such a recycling system.

Structural and electrochemical properties of recycled active electrodes from spent lead acid battery and modified with different manganese dioxide contents

Samples of MnO2 incorporated into active electrodes structure of the disassembled car batteries were prepared by classical melt-quenching method. The effect of MnO2 concentration on host network were investigated by X-ray diffraction (XRD) analysis, InfraRed (IR), UltraViolet-Visible (UV–Vis), Photoluminescence (PL) and Electron Paramagnetic Resonance (EPR) spectroscopy, measurements of Cyclic Voltammetry (VC).X-ray diffractograms show the presence of the metallic lead in the cubic structure and small amounts of PbO2 crystalline phase with the orthorhombic structure in the metallic samples.Combining all of the outputs from different characterizations, we can conclude that the amount of MnO2 incorporated into structure of the recycled active electrodes has effect on the number of non-bridging oxygen atoms that determines the role of MnO2 as a modifier/network former. At lower MnO2 contents, the doping breaks PbOPb bonds producing the formation of [MnO6] structural units in which the Mn+2 ions are in octahedral symmetry, gap energy value increases and the effect of luminescence is quenched. At higher MnO2 content, MnO2 plays a network former role, joins the vitroceramic network as [MnO4] and [MnO6] structural units and the PL intensity increases.The sample doped with small MnO2 content (x = 5mol%) used as working electrode in the measurements of cyclic voltammetry shows a good reversibility of the voltammogram, also improved the electrochemical properties, namely an increased stability in acidic electrolyte environments and offers an alternative for obtaining of electrodes for rechargeable batteries.

Lead‐Carbon Batteries: Synthesis of Nanostructured PbO@C Composite Derived from Spent Lead‐Acid Battery for Next‐Generation Lead‐Carbon Battery (Adv. Funct. Mater. 9/2018)

Lead‐Carbon Batteries: Synthesis of Nanostructured PbO@C Composite Derived from Spent Lead‐Acid Battery for Next‐Generation Lead‐Carbon Battery (Adv. Funct. Mater. 9/2018)

Removing antimony from waste lead storage batteries alloy by vacuum displacement reaction technology

With the wide application of lead acid battery, spent lead acid battery has become a serious problem to environmental protection and human health. Though spent battery can be a contaminant if not handled properly, it is also an important resource to obtain refined lead. Nowadays, the Sb-content in lead storage batteries is about 0.5–3 wt%, which is higher than the Sb-content in the crude lead. However, there are few reports about the process of removing antimony from high-antimony lead bullion. In this study, vacuum displacement reaction technology, a new process for removing antimony from high-antimony lead melts, was investigated. During this process, lead oxide was added to the system and antimony from lead melts was converted into antimony trioxide, which easily was evaporated under vacuum so that antimony was removed from lead melts. The experimental results demonstrated that Sb-content in lead melts decreased from 2.5% to 23 ppm under following conditions: mass ratio of PbO/lead bullion of 0.33, residual gas pressure of 30 Pa, melt temperature of 840 °C, reaction time of 60 min. The distillate gotten can be used as by-product to produce antimony white. Moreover, this study is of importance to recycling of waste lead storage batteries alloy.

Spent Lead-Acid Batteries Crushing Mechanical Properties and Impact Crushing Effect

The spent lead-acid battery contains a large amount of lead metal and waste acid. If not treated or simply treated, it will cause serious environmental pollution and even endanger human health. The paper focuses on the recovery of valuable resources such as lead paste and plastic by replacing chemical methods with physical ones, which the bending performance was tested with electronic universal testing machine and the impact performance measured with plastic pendulum impact testing machine. At the same time, a self-designed crusher is also used for impact crushing. The test results showed that the plastic shell is hard and brittle and has strong resistance to bending, but its impact resistance is weak. The spent lead-acid batteries were crushed by self-designed impact crusher. In the broken products, the grids and fiber separators were distributed between 2.2-0.5 mm in diameter, while plastics mainly over 10 mm and lead paste mainly below 0.1 mm. The XRD results show that the lead in each particle size has different forms and contents of lead. Different comminution experiments show that the appropriate process parameters can achieve the existence of valuable resources such as plastics, grids, and lead pastes in spent lead-acid batteries according to their shape and size, which helps the subsequent sorting and recovery of valuable materials.

PbSO4 Leaching in Citric Acid/Sodium Citrate Solution and Subsequent Yielding Lead Citrate via Controlled Crystallization

Lead citrate is a key precursor for the green recycling of spent lead acid battery paste in a citric acid/sodium citrate (CA/SC) solution. In this study, the main paste component, PbSO4, was leached and crystallized to yield lead citrate. Results showed that the leaching of PbSO4 in citric acid/sodium citrate solution was remarkably enhanced by an increase in temperature from 35 °C to 95 °C and an increase in sodium citrate (SC) concentration from 50 to 650 g/L. In comparison, increasing the citric acid/sodium citrate molar ratio inhibited this leaching. Controlled crystallization through cooling the solution or adjusting the pH of the solution can effectively produce lead citrate crystals. The X-ray diffraction patterns of four products obtained in a comparison test were all consistent with Pb3(C6H5O7)2. However, the scanning electron microscopy analysis suggested that the morphology was distinct from rods to sheets, which were mainly affected by the temperature variation.

Developing Electrolyte for a Soluble Lead Redox Flow Battery by Reprocessing Spent Lead Acid Battery Electrodes

The archival value of this paper is the investigation of novel methods to recover lead (II) ions from spent lead acid battery electrodes to be used directly as electrolyte for a soluble lead flow battery. The methods involved heating electrodes of spent lead acid batteries in methanesulfonic acid and hydrogen peroxide to dissolve solid lead and lead dioxide out of the electrode material. The processes yielded lead methanesulfonate, which is an electrolyte for the soluble lead acid battery. The lead (II) ions in the electrolyte were identified using Inductively Coupled Plasma Mass Spectroscopy and their electrochemistry confirmed using cyclic voltammetry. The concentration of lead (II) ions was determined and it was found that using the higher concentration of hydrogen peroxide yielded the highest concentration of lead (II) ions. The method was therefore found to be sufficient to make electrolyte for a soluble lead cell.

Preparing ultrafine PbS powders from the scrap lead-acid battery by sulfurization and inert gas condensation

A novel method for preparing ultrafine PbS powders involving sulfurization combined with inert gas condensation is developed in this paper, which is applicable to recycle Pb from lead paste of spent lead-acid batteries. Initially, the effects of the evaporation and condensation temperature, the inert gas pressure, the condensation distance and substrate on the morphology of as-obtained PbS ultrafine particles are intensively investigated using sulfur powders and lead particles as reagents. Highly dispersed and homogeneous PbS nanoparticles can be prepared under the optimized conditions which are 1223 K heating temperature, 573 K condensation temperature, 100 Pa inert gas pressure and 60 cm condensation distance. Furthermore, this method is successfully applied to recycle Pb from the lead paste of spent lead acid battery to prepare PbS ultrafine powders. This work does not only provide the theoretical fundamental for PbS preparation, but also provides a novel and efficient method for recycling spent lead-acid battery with high added-value products.

A low-cost green technology for recovering lead paste and lead-alloy grid materials for spent lead acid batteries

ABSTRACTA new method, currently under industrial trial, consists in dissolving the hard-to-recover lead-bearing active components of battery paste in an aqueous solution of carboxylic acids, derived from plants, and precipitating the lead as organic crystal plates. The lead organic material is self-combusting, generating leady oxide as desired for direct new battery paste preparation. The organics, embodied in the precursor, serve as the fuel by combustion to aid calcination. The lead grids are refined separately using heat from the first process. The use of acids from plants which is produced using a renewable stock, not only as a reagent but also as source of energy, will result in a very low-carbon footprint. Since economy of scale is not a limiting factor, such a technology will offer the vision for nucleating/retrofitting many small-scale lead battery operations in rural industry in rapidly growing economies.

Structural and electrochemical investigations of the electrodes obtained by recycling of lead acid batteries

The lead acid batteries are widely used in automobile and provide spent electrodes composed of PbO2/PbSO4 and Pb/PbSO4. Today, batteries are treated and recycled using the pyrometallurgical and hydrometallurgical techniques. However, these techniques have some important disadvantages: i) the small lead recovery rate (due to the rapid oxidation of the electrolytic Pb powder in the atmosphere); ii) the important amount of energy and time spent to convert oxides and sulfates into metal, which is subsequently reconverted to oxides; iii) the harmful emissions and their negative environmental impact.In this work, we propose a method of recycling batteries by a melt quenching route in order to improve the present practice. Is the melt quenching method a new eco-innovative approach for lead recycling of spent lead acid batteries? We think that yes, since economically is more favorable (in terms of low production cost, energy and time saving) and environmentally more friendly.Focus was addressed on both the structural characterization (by X-ray diffraction) of the samples obtained by melt quenching of spent electrodes proceeded from car batteries, as well as on their electrochemical and electrical characterization by cyclic voltammetry and electrochemical impedance spectroscopy as potential raw materials in obtaining new and more performing battery electrodes. Our results suggest that the increase of Pb concentration in the recycled electrodes implies the formation of a regulated lead sulfate layer in the oxidation process and the dissolving of PbSO4 crystals followed by the hydrogen evolutions in reduction process of lead ions.

Power Failure: The Battered Legacy of Leaded Batteries

Viewpoint pubs.acs.org/est Power Failure: The Battered Legacy of Leaded Batteries Oladele A. Ogunseitan* Program in Public Health and School of Social Ecology, University of California, Irvine, California 92697, United States flow of toxic products intact. The U.S. has not ratified the Basel Convention. Rather, lead-acid batteries are regulated under the Resource Conservation and Recovery Act (RCRA) of 1976, as part of negotiations to harmonize U.S. policies with initiatives of the Organization for Economic Cooperation and Develop- ment. 4 Individual states in the U.S. stipulate either mandatory or voluntary cash deposits, typically $5−10, for used batteries returned by consumers at the point of purchase of a new lead- acid battery. The U.S. Environmental Protection Agency (EPA) considers the high “recycling” rate of lead-acid battery as evidence of successful public-private partnerships in pollution prevention policy. 4 The apparent success of the retailer take-back program masked growing concerns about pollution and health impacts created by battery recycling in developing countries, until similar problems emerged within continental U.S., exemplified by a recent case in California. In February, 2016, California Governor Jerry Brown proposed spending $176.6 million to accelerate the testing and cleanup of thousands of lead- contaminated homes surrounding the troubled Exide battery recycling facility in the Vernon district of Los Angeles, which is predominantly populated by families in the lower socio- he history of automobiles is inextricable from the story of economic category. 5 The funds will support testing 10 000 one of the most pervasive toxic chemical exposures in homes within 1.7 miles of the closed facility and the removal of modern human history. Globally, billions of people were lead-contaminated soil from about 2500 homes where levels poisoned by lead (Pb) between 1921, when General Motors pose the greatest risk of poisoning. 5 Corporation introduced tetraethyl lead as an antiknock agent in Unfortunately, the Exide-linked pollution in Los Angeles is gasoline-powered cars, until 2015, when leaded gasoline was only a “tip of the iceberg” in terms of global impacts of lead scheduled to be phased out in Algeria, the last country still poisoning from batteries. The international market for using leaded gasoline. reclaiming lead is growing rapidly, 2 and battery-recycling The elimination of lead from gasoline is one of the greatest operations can be found in almost every city in the developing milestones in public health. Regulatory policies were world. Battery smelting operations are often located in densely instrumental in achieving the phase-out of leaded gasoline, populated areas with inadequate pollution controls. Regulatory and these were informed by incontrovertible scientific evidence policies that supported high rates of battery recycling also that there are no safe levels of exposure to lead and that dampened interest in developing safer lead-free alternatives. children are particularly susceptible to its adverse health The emergence of hybrid and full electric automobiles has effects. 1 Unfortunately, lead remains a tenacious toxicant spurred the development of advanced lithium-ion batteries, but because of ubiquitous lead-acid batteries that power more these may have their own safety concerns. than a billion cars on the road today. T EMPOWERING INNOVATION California’s landmark Safer Consumer Products Law of 2013 requires manufacturers to seek safer alternatives to harmful chemical ingredients in widely used products. At the federal level, the U.S. EPA uses alternatives analysis (AA) as part of chemical action plans in its chemical management program. Similarly, the European Union’s Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) program imposes alternatives analysis obligations upon certain partic- A FAILED POLICY ON RECYCLING In 2015, ∼90% of 1.62 million tons of lead consumed in the United States was for production of >94.1 million lead-acid batteries. 2 These batteries have an international life cycle: during the first 8 months of 2015, 19.3 million spent lead-acid batteries, containing an estimated 167 000 tons of lead, 2 were exported to low- and middle income countries where they fed hazardous industries for materials recovery. Spent lead-acid batteries are recognized as hazardous waste under Annex VIII of the United Nation’s Basel Convention on the Control of Transboundary Hazardous Wastes and Their Disposal. 3 However, several loopholes keep the international © 2016 American Chemical Society Received: June 24, 2016 Published: July 28, 2016 DOI: 10.1021/acs.est.6b03174 Environ. Sci. Technol. 2016, 50, 8401−8402

Electrochemical property of α-PbO prepared from the spent negative powders of lead acid batteries

To make full and economic use of the spent lead acid batteries (LABs), we have invented a novel route to separate their negative electrode material from positive one, which are respectively used to fabricate α-PbO for new LABs. This paper reports preparation and electrochemical property of α-PbO from the spent negative material which is compose of PbSO4 (the major phase) and Pb (the minor phase). To make things simpler, pure PbSO4 is firstly used as the model compound and desulfated with (NH4)2CO3 to obtain PbCO3, which is then calcined in air at different temperatures to produce PbO. At 450 °C, the calcination produces pure α-PbO that discharges a capacity of 98.6 mAh g−1 at the current density of 120 mA g−1 after 50 charging and discharging cycles of 100 % DOD. By using the same procedures, the real spent negative powder is also treated to produce pure α-PbO, which discharges a similar capacity of 100 mAh g−1 at 120 mA g−1. This is 25 % higher than that of industrial leady oxide. These results show that the small amount of metallic lead has little effect on the treatment.

Effect of pH on desulphurization of spent lead paste via hydrometallurgical process

The effect of pH was investigated in a hydrometallurgical method for recycling spent lead-acid batteries with citric acid. The pH in this novel procedure was adjusted with a cheap and conveniently available alkalescent reagent-ammonia. The desulphurization efficiency of spent lead paste could be increased dramatically up to 99wt% at a weaker acidic pH of 5.5, compared with only 20wt% without pH adjustment using a fixed leaching at more acidic pH of 2.1 for the duration time of 180 min. The mechanism of the improvement of desulphurization efficiency at adjusted weaker acidic pH was proposed as the demolition of the core-shell structure. The dissolution of lead citrate (shell) will make the lead sulphate particles (core) released and available to react. The chemical formula of the lead citrate product was either Pb(C6H6O7)·H2O at more acidic pH of 3.3, or Pb3(C6H5O7)2·3H2O at weaker acidic pH of 5.5 and 6.2. The pH value will also notably affect the final concentrations of the main impurities in the obtained lead citrate products. A more acidic pH was more favorable for the elimination of the main impurities such as Fe, Ba, Sb, Cu, Zn and Al, by forming soluble species that remained in the leaching solution, which results in cleaner solid lead citrate products. This study has emphasized the availability of pH as a key factor in a novel hydrometallurgical route for recycling spent lead acid batteries.

Preparation of High Purity Lead Oxide from Spent Lead Acid Batteries via Desulfurization and Recrystallization in Sodium Hydroxide

This paper reports a new method of direct recovery of highly pure lead oxide (PbO) from waste lead pastes and lead grids of spent lead–acid batteries via catalytic conversion, desulfurization, and recrystallization processes in sequence. On the basis of the analytical results of lead (Pb) and lead dioxide (PbO2) contents in the scrap lead paste, a certain amount of waste lead grid was used as a reductant to transform the excess PbO2 into lead sulfate (PbSO4). This paper systematically studies the influence of the concentration of sulfuric acid (H2SO4) and catalyst and the reaction temperature on the catalytic process. The desulfurization of the obtained PbSO4 and the recrystallization of PbO in sodium hydroxide (NaOH) solutions of different concentrations are also investigated. Furthermore, electrochemical experimental results show that the prepared α-PbO with high purity provides slightly superior electrochemical performance to the existing lead oxide obtained by the Shimadzu ball-milling method during t...

Reductive smelting of spent lead–acid battery colloid sludge in a molten Na2CO3 salt

Lead extraction from spent lead–acid battery paste in a molten Na2CO3 salt containing ZnO as a sulfur-fixing agent was studied. Some influencing factors, including smelting temperature, reaction time, ZnO and salt dosages, were investigated in detail using single-factor experiments. The optimum conditions were determined as follows: T = 880°C; t = 60 min; Na2CO3/paste mass ratio = 2.8:1; and the ZnO dosage is equal to the stoichiometric requirement. Under the optimum conditions, the direct recovery rate of lead reached 98.14%. The results suggested that increases in temperature and salt dosage improved the direct recovery rate of lead. XRD results and thermodynamic calculations indicated that the reaction approaches of lead and sulfur were PbSO4→Pb and PbSO4→ZnS, respectively. Sulfur was fixed in the form of ZnS, whereas the molten salt did not react with other components, serving only as a reaction medium.

Recovery of lead from lead paste in spent lead acid battery by hydrometallurgical desulfurization and vacuum thermal reduction

Lead sulfate, lead oxides and lead metal are the main component of lead paste in spent lead acid battery. When lead sulfate was desulfurized and transformed into lead carbonate by sodium carbonate, lead metal and lead oxides remained unchanged. Lead carbonate is easily decomposed to lead oxide and carbon dioxide under high temperature. Namely, vacuum thermal process is the reduction reaction of lead oxides. A compatible environmental process consisted of hydrometallurgical desulfurization and vacuum thermal reduction to recycle lead was investigated in this research. Lead paste was firstly desulfurized with sodium carbonate, by which, the content of sulfur declined from 7.87% to 0.26%. Then, the desulfurized lead paste was reduced by charcoal under vacuum. Under the optimized reaction conditions, i.e., vacuum thermal reduction at temperature 850°C under 20Pa for 45min, a 22.11×10−2gcm−2min−1 reduction rate, and a 98.13% direct recovery ratio of fine lead (99.77%) had been achieved, respectively.

Producing hierarchical porous carbon monoliths from hydrometallurgical recycling of spent lead acid battery for application in lithium ion batteries

An environmentally clean process to recycle the paste from a spent lead acid battery (LAB) is further developed to produce a porous carbon anode material for a lithium ion battery (LIB) which is under increasing focus as the solution for future energy storage and distribution networks.