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[Display omitted] • A green and efficient microwave-assisted leaching is proposed for metal recovery. • Citric acid shows a superior performance as a reductant in leaching efficiency. • Nearly 100 % metals are recovered using 0.2 mol/L H 2 SO 4 and 0.05 mol/L citric acid. • Kinetic analysis is performed to understand microwave-assisted leaching process. The management and sustainable recycling of spent lithium-ion batteries (LIBs) holds critical importance from both economic and environmental standpoints. H 2 O 2 and ascorbic acid are widely used inorganic and organic reductants in the hydrometallurgical process for battery recycling. In this study, citric acid, as a reductant, was found to have superior metal leaching efficiencies under microwave-assisted leaching than H 2 O 2 and ascorbic acid. The enhanced performance was attributed not only to the inherent reducing property of citric acid but also to the chelation of citric acid with Cu and Fe, resulting in the formation of reductive radicals under microwave. The effect of acid type, H 2 SO 4 concentration, citric acid concentration, solid-liquid (S/L) ratio, reaction time, and temperature were investigated. 99.5 % of Li, 99.7 % of Mn, 99.5 % of Co, and 99.3 % of Ni were leached from spent lithium nickel manganese cobalt oxides (NCM) battery black mass using 0.2 mol/L H 2 SO 4 and 0.05 mol/L citric acid at 120 °C for 20 min with a fixed S/L ratio of 10 g/L in the microwave-assisted leaching process. Leaching kinetic results were best fitted with the Avrami model, suggesting that the microwave-assisted leaching process was controlled by diffusion. The leaching activation energies of Li, Mn, Co, and Ni were 30.11 kJ/mol, 27.48 kJ/mol, 21.32 kJ/mol, and 33.29 kJ/mol, respectively, providing additional evidence that supports the proposed diffusion-controlled microwave-assisted leaching mechanism. This method provided a green and efficient solution for spent LIBs recycling. [ABSTRACT FROM AUTHOR]

The development of hydrometallurgical recycling processes for lithium-ion batteries is challenged by the heterogeneity of the electrode powders recovered from end-of-life batteries via physical methods. These electrode materials, known as black mass, vary in composition, containing differing amounts of nickel, manganese, and cobalt (NMC), as well as other chemicals, such as lithium iron phosphate (LFP). This study presents the results of the hydrometallurgical treatment of mixed NMC and LFP black masses aimed at creating flexible recycling processes. This approach leverages the reducing power of LFP to optimize the leach liquor composition for re-synthesizing NMC precursors. In particular, the leaching conditions were optimized based on the LFP content in the solid feed to maximize the extraction of key metals (Ni, Mn, Co, and Li). The leaching solid residue, graphite, was treated and characterized as a secondary raw material for new anode preparation. Iron phosphate was recovered by increasing the pH of the leach liquor, and the NMC precursors were obtained via coprecipitation. This process achieved a recycling rate of 51%, based on the black mass input and the mass of recovered elements in the output products. Additionally, substituting LFP scraps as the reducing agent in place of H2O2 reduced the recycling process's environmental impact by avoiding 1.7 tons of CO2-equivalent emissions per ton of NMC black mass. [ABSTRACT FROM AUTHOR]

Wastes from spent batteries are a secondary source of raw materials. To ensure this, it is mandatory to design sustainable and low-cost processes. In the case of alkaline and zinc–carbon-based batteries, the high content of Zn and Mn makes them of interest in the development of fertilizers. The main objective of this research is to study the fertilizers production from spent zinc-based batteries, using sulfuric acid, citric acid (CIT) and glycine (GLY) solutions as leaching agents. Leaching with glycine at alkaline pHs shows a high selectivity of Zn over Mn, whereas the use of citric and sulfuric solutions leads to recoveries of Zn and Mn. Solutions with the highest Zn recoveries were tested in sand columns. Commercial ZnSO4 heptahydrate was used as a control. For sulfuric acid, two solutions (H2SO4 2M and 0.25M) were used. The elution of leached Zn and Mn in sand columns depended on the solution added. The Zn-Mn-CIT treatment showed a slight but steady increase in the leachates, reaching 70% and 75% of the total leached Zn and Mn, respectively, in the medium term. The Zn-Mn-H2SO4 2M and ZnSO4 treatments showed a similar behavior in Zn release. Both Zn-Mn-GLY and Zn-Mn-H2SO4 0.25M treatments showed similar amounts of leached Mn in the medium term (77% of total leached Mn), differing in the leached Zn. Solutions from the leaching of spent black mass batteries, especially Zn-Mn-CIT or Zn-Mn-GLY, showed promising behavior as fertilizer from the point of view of Zn and Mn availability as nutrients. [ABSTRACT FROM AUTHOR]

The development of hydrometallurgical recycling processes for lithium-ion batteries is challenged by the heterogeneity of the electrode powders recovered from end-of-life batteries via physical methods. These electrode materials, known as black mass, vary in composition, containing differing amounts of nickel, manganese, and cobalt (NMC), as well as other chemicals, such as lithium iron phosphate (LFP). This study presents the results of the hydrometallurgical treatment of mixed NMC and LFP black masses aimed at creating flexible recycling processes. This approach leverages the reducing power of LFP to optimize the leach liquor composition for re-synthesizing NMC precursors. In particular, the leaching conditions were optimized based on the LFP content in the solid feed to maximize the extraction of key metals (Ni, Mn, Co, and Li). The leaching solid residue, graphite, was treated and characterized as a secondary raw material for new anode preparation. Iron phosphate was recovered by increasing the pH of the leach liquor, and the NMC precursors were obtained via coprecipitation. This process achieved a recycling rate of 51%, based on the black mass input and the mass of recovered elements in the output products. Additionally, substituting LFP scraps as the reducing agent in place of H2O2 reduced the recycling process’s environmental impact by avoiding 1.7 tons of CO2-equivalent emissions per ton of NMC black mass.

The demand for lithium-ion batteries (LIBs) has dramatically increased in recent years due to their application in various electronic devices and electric vehicles (EVs). Great amount of LIB waste is generated, most of which ends up in landfills. LIB wastes contain substantial amounts of critical metals (such as Li, Co, Ni, Mn, and Cu) and can therefore serve as valuable secondary sources of these metals. Metal recovery from the black mass (shredded spent LIBs) can be achieved via bioleaching, a microbiology-based technology that is considered to be environmentally friendly, due to its lower costs and energy consumption compared to conventional pyrometallurgy or hydrometallurgy. However, the growth and metabolism of bioleaching microorganisms can be inhibited by dissolved metals. In this study, the indigenous acidophilic chemolithotrophs in a sediment from a highly acidic and metal-contaminated mine pit lake were enriched in a selective medium containing iron, sulfur, or both electron donors. The enriched culture with the highest growth and oxidation rate and the lowest microbial diversity (dominated by Acidithiobacillus and Alicyclobacillus spp. utilizing both electron donors) was then gradually adapted to increasing concentrations of Li+, Co2+, Ni2+, Mn2+, and Cu2+. Finally, up to 100% recovery rates of Li, Co, Ni, Mn, and Al were achieved via two-step bioleaching using the adapted culture, resulting in more effective metal extraction compared to bioleaching with a non-adapted culture and abiotic control. [ABSTRACT FROM AUTHOR]

The increasing significance of batteries in the 21st century and the challenges posed by the anticipated surge in end-of-life batteries, particularly within the European context, are examined in this study. Forecasts predict a notable escalation in battery waste, necessitating a focus on the recycling of black mass (BM)—a complex and hazardous byproduct of the battery recycling process. Employing systematic analysis, this research investigates the hazardous nature of BM derived from various battery types. The study underscores the urgent need for definitive legislative classification of BM's hazardous properties (HPs), in accordance with European regulations. This comprehensive examination of BM's HPs contributes significantly to the understanding of BM recycling complexities, proving essential for industry stakeholders and guiding future developments in this field. Additionally, the study explores innovative technologies and strategies that could improve recycling efficiency and reduce associated risks. A pivotal finding of this investigation is the inherently hazardous nature of BM, leading to the recommendation that BM should be classified at a minimum under the "HP3—Flammable" category. This discovery underscores the critical need for stringent management protocols and robust regulatory frameworks to address the burgeoning challenge of battery waste in Europe. [ABSTRACT FROM AUTHOR]

The early-stage lithium recovery (ESLR) process associates thermal treatment of the black mass from lithium-ion batteries (LIB) with subsequent leaching, especially with water, targeting Li recovery in the first step of the process chain as lithium carbonate. The validation of ESLR has resulted in high Li efficiencies; however, currently, researchers have not yet been established the optimum parameters, which brings uncertainties to a further upscale. Based on that, four parameters, including different black masses previously thermally treated in the industry, were investigated in a leaching step in laboratory scale targeting Li and F leaching efficiencies. Through ANOVA statistical analysis, regression equations of the leaching efficiencies for both elements were generated, which supports an optimization study. The optimum parameters were then transferred to an upscale 100 L leaching trial and evaluated. The results in laboratory scale showed that Li maximization and F minimization were achieved at an S/L ratio of 30 g/L, 80 °C, and 6 L/min of CO2 gas addition, as well as with a sample of bigger particle size and probably more efficient thermal treatment. However, the upscale result with the same parameters showed a lower Li leaching efficiency, which is related to the poor geometric similarity between laboratory and upscale reactors. [ABSTRACT FROM AUTHOR]

• Investigation of different cell chemistries and designs on the depth of discharge. • Properties of functional units depend on the depth of discharge. • Separation of separator foil as single fraction is not always feasible. • Black mass of cells discharged into pole reversal shows higher Cu content. • Influence of discharge is independent of cell chemistry or cell design. Prior to the mechanical processing, discharging is necessary to prevent hazards. While the discharging process, different phenomena can occur changing the characteristics of the functional units of LIB. This study reveals the influence on the mechanical recycling and the obtained material when different discharge levels are used for various cells differing in their cell chemistry. It shows that for different cells, for example, copper deposits happen on the cathode as well as active material deposits on the separator foil. These new properties deteriorate the black mass quality and show contamination of the products with other material streams. It is being tested whether established sub-processes are suitable. However, it becomes clear that further recycling steps (e.g. flotation, hydrometallurgy) can be influenced as well as their product quality and element specific yield. [ABSTRACT FROM AUTHOR]

• Direct, selective leaching of Li from industrial-grade LIBs powder for the first time. • Omission of pre-leach powder separation shortens the process and reduces cost. • The role and mechanism of anode carbon in promoting selectivity were revealed. • Excellent selectivity and high Li leaching efficiency (Li greater than 97%, others < 1%). • Post-leaching solution is alkaline, circumventing neutralization for subsequent work. Demand for lithium-ion batteries (LIBs) is projected to maintain unprecedented acceleration for decades, towards satisfying international climate and source objectives. LIB wastes pose a threat to the environment, but also may be considered a strategic, high-grade resource. Yet, recycling the black mass of waste LIBs, which contains plastic, C, Li, Fe, Ni, Co, Mn, Cu, and Al, is very complex. Herein, the direct selective leaching of Li from the industrial-grade black mass powder of waste LIBs is proposed for the first time. Results demonstrated that the leaching efficiency of Li is shown to exceed 97%, while other metals remain below 1%. The mechanism of selective leaching was also investigated in this study. Under the experimental conditions, Fe is not leached out and remains in the form of solid FePO 4. As for other impurity metal elements, they are removed from the solution due to the alkaline environment of the post-leaching solution and the adsorption effect of the anodic carbon. Furthermore, the alkaline post-leaching solution can avoid the neutralizing stage before the precipitation of lithium salts. This highly efficient and Li-selective leaching strategy offers a broadly applicable approach to reclaiming critical energy minerals from the black mass of wasted LIBs. [ABSTRACT FROM AUTHOR]

The processing and extraction of critical metals from black mass is important to battery recycling. Separation and recovery of critical metals (Co, Ni, Li, and Mn) from other metal impurities must yield purified metal salts, while avoiding substantial losses of critical metals. Solvent extraction in batch experiments were conducted using mixed metal sulphates obtained from the leach liquor obtained from spent and shredded lithium-ion batteries. Selective extraction of Mn2+, Fe3+, Al3+ and Cu2+ from simulated and real leached mixed metals solution was carried out using di-2-ethylhexylphophoric acid (D2EPHA) and Cyanex-272 at varying pH. Further experiments with the preferred extractant (D2EPHA) were performed under different conditions: changing the concentration of extractant, organic to aqueous ratio, and varying the diluents. At optimum conditions (40% v/v D2EPHA in kerosene, pH 2.5, O:A = 1:1, 25 °C, and 20 min), 85% Mn2+, 98% Al3+, 100% Fe3+, and 43% Cu2+ were extracted with losses of only trace amounts (<5.0%) of Co2+, Ni2+, and Li+. The order of extraction efficiency for the diluents was found to be kerosene > Exxal-10 >>> dichloromethane (CH2Cl2) > toluene. Four stages of stripping of metals loaded on D2EPHA were performed as co-extracted metal impurities were selectively stripped, and a purified MnSO4 solution was produced. Spent extractant was regenerated after Fe3+ and Al3+ were completely stripped using 1.0 M oxalic acid (C2H2O4). [ABSTRACT FROM AUTHOR]

The literature indicates that utilizing pyrometallurgical methods for processing spent LiCoO2 (LCO) batteries can lead to cobalt recovery in the forms of Co3O4, CoO, and Co, while lithium can be retrieved as Li2O or Li2CO3. However, the technology's high energy consumption has also been noted as a challenge in this recovery process. Recently, an innovative and sustainable approach using microwave (MW) radiation has been proposed as an alternative to traditional pyrometallurgical methods for treating used lithium-ion batteries (LiBs). This method aims to address the shortcomings of the conventional approach. In this study, the treatment of the black mass (BM) from spent LCO batteries is explored for the first time using MW–materials interaction under an air atmosphere. The research reveals that the process can trigger carbothermic reactions. However, MW makes the BM so reactive that it causes rapid heating of the sample in a few minutes, also posing a fire risk. This paper presents and discusses the benefits and potential hazards associated with this novel technology for the recovery of spent LCO batteries and gives information about real samples of BM. The work opens the possibility of using a microwave for raw material recovery in spent LIBs, allowing to obtain rapid and more efficient reactions. [ABSTRACT FROM AUTHOR]

With the increasing number of electric vehicles (EVs) rises the need to recycle their used lithium-ion batteries (LIBs). During the mechanical process of the recycling of the LIB cells, a fine fraction, the so-called black mass, is created. This black mass consists mostly of the coatings originating from the cells' electrodes and residues from the electrolyte, together with a low amount of Al and Cu from the crushed current collector foils. The amount of black mass as well as its composition is influenced by the chosen grid size at the crusher discharge. To reduce solvent emissions during the recycling process, a thermal pre-treatment can be added before crushing, which also influences the black mass and its properties due to changes in the adhesion between electrode foils and coating. This study investigates the influence of the crusher settings as well as the pre-treatment temperatures to find an optimum between the recovery of the coating and conductive salt, while limiting the amount of Al and Cu in the black mass. [ABSTRACT FROM AUTHOR]

Many countries have started their transition to a net-zero economy. Lithium-ion batteries (LIBs) play an ever-increasing role towards this transition as a rechargeable energy storage medium. Initially, LIBs were developed for consumer electronics and portable devices but have seen dramatic growth in their use in electric vehicles (EVs) and via the gradual uptake in battery energy storage systems (BESSs) over the last decade. As such, critical metals (Li, Co, Ni, and Mn) and chemicals (polymers, electrolytes, Cu, Al, PVDF, LiPF6, LiBF4, and graphite) needed for LIBs are currently in great demand and are susceptible to global supply shortages. Dramatic increases in raw material prices, coupled with predicted exponential growth in global demand (e.g., United States graphite demand from 2022 7000 t to ~145,000 t), means that LIBs will not be sustainable if only sourced from raw materials. LIBs degrade over time. When their performance can no longer meet the requirement of their intended application (e.g., EVs in the 8–12 year range), opportunities exist to extract and recover battery materials for re-use in new batteries or to supply other industrial chemical sectors. This paper compares the challenges, barriers, opportunities, and successes of the United States of America and Australia as they transition to renewable energy storage and develop a battery supply chain to support a circular economy around LIBs. [ABSTRACT FROM AUTHOR]

Lithium is a key element in reducing mobility-induced emissions. However, processes aimed at producing lithium from hard rock mining are based on the usage of large amounts of chemicals. Additionally, only a small quantity of the mined mineral concentrates is actually valorized. In contrast, the COOL process (CO2 Leaching process) is a process that makes use of water and carbon dioxide to leach lithium from any silicate mineral, making geopolymers from the residues. On the other hand, the COOL process enables the recovery of lithium from pretreated spent lithium-ion batteries. The leaching step has been investigated concerning the selective mobilization of lithium. Further attention was brought to the mobilization of potentially disturbing ions such as fluoride, aluminum, and silicon. It was found that the CO2 leaching step is indeed suitable for the selective mobilization of lithium. Up to 65% of lithium mobilization was achieved without adding any additives and 78% by adding Na2CO3. Fluoride and silicon mobilization could be addressed by heating zinnwaldite under a wet atmosphere respectively under the addition of a carbonate. Concerning secondary resources, up to 95% of lithium could be leached from black mass, and the residue was then leached and the leach liquor separated by liquid-liquid extraction to yield the heavy metals in high recovery and selectivity. Overall, the COOL process enables the recovery of lithium from different feedstocks and valorizes the residues from the lithium leaching. This makes the COOL process a universal approach to lithium recovery. [ABSTRACT FROM AUTHOR]

Black mass is the industry term applied to end-of-life (EoL) lithium-ion batteries that have been mechanically processed for potential use as a recycled material to recover the valuable metals present, including cobalt, lithium, manganese, nickel and copper. A significant challenge to the effective processing of black mass is the complexity of the feed material. Two samples of black mass from a European source were analysed using a combination of methods including automated SEM-EDS (AMICS) to characterise and quantify the phases present and particle chemistry. Micro X-CT imaging, overlain onto automated mineralogy images, enabled the 3D morphology of the particles to be determined. Micro-XRF was used to map the copper, nickel, manganese and cobalt-bearing phases. Since Li cannot be detected using SEM-EDS, its abundance was semi-quantified using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The integration of these complimentary analytical methods allowed for detailed phase characterisation, which may guide the potential hydrometallurgical or pyrometallurgical recycling routes and chemical assaying. [ABSTRACT FROM AUTHOR]

The increasing significance of batteries in the 21st century and the challenges posed by the anticipated surge in end-of-life batteries, particularly within the European context, are examined in this study. Forecasts predict a notable escalation in battery waste, necessitating a focus on the recycling of black mass (BM)—a complex and hazardous byproduct of the battery recycling process. Employing systematic analysis, this research investigates the hazardous nature of BM derived from various battery types. The study underscores the urgent need for definitive legislative classification of BM’s hazardous properties (HPs), in accordance with European regulations. This comprehensive examination of BM’s HPs contributes significantly to the understanding of BM recycling complexities, proving essential for industry stakeholders and guiding future developments in this field. Additionally, the study explores innovative technologies and strategies that could improve recycling efficiency and reduce associated risks. A pivotal finding of this investigation is the inherently hazardous nature of BM, leading to the recommendation that BM should be classified at a minimum under the “HP3—Flammable” category. This discovery underscores the critical need for stringent management protocols and robust regulatory frameworks to address the burgeoning challenge of battery waste in Europe.

The early-stage lithium recovery (ESLR) process associates thermal treatment of the black mass from lithium-ion batteries (LIB) with subsequent leaching, especially with water, targeting Li recovery in the first step of the process chain as lithium carbonate. The validation of ESLR has resulted in high Li efficiencies; however, currently, researchers have not yet been established the optimum parameters, which brings uncertainties to a further upscale. Based on that, four parameters, including different black masses previously thermally treated in the industry, were investigated in a leaching step in laboratory scale targeting Li and F leaching efficiencies. Through ANOVA statistical analysis, regression equations of the leaching efficiencies for both elements were generated, which supports an optimization study. The optimum parameters were then transferred to an upscale 100 L leaching trial and evaluated. The results in laboratory scale showed that Li maximization and F minimization were achieved at an S/L ratio of 30 g/L, 80 °C, and 6 L/min of CO2 gas addition, as well as with a sample of bigger particle size and probably more efficient thermal treatment. However, the upscale result with the same parameters showed a lower Li leaching efficiency, which is related to the poor geometric similarity between laboratory and upscale reactors.

Due to the finite availability of fossil fuels, enormous efforts have been made to replace gasoline automobiles with electric transportation vehicles. The recycling of dead batteries, which is a critical energy resource component of today's electric vehicles (EVs), is required for the development of more sustainable EVs sector. Despite rising return flows, less attention has been placed on the recycling of LFP batteries due to their low proportion of value aided metals. It is critical to create cost-effective lithium extraction technologies and cathode material restoration procedures to enable the long-term and stable growth of the LFP battery and EV industries. The current state of the LFP battery market along with electrochemical properties and synthetic routes is briefly discussed in this report. Moreover, recycling procedures for LIBs are examined, and their relevance for LFP batteries is evaluated. Individually customizable procedures such as mechanical pre-treatment of cells, hydrometallurgical upscaling of the active cathode material appears to be the most efficient method option for LFP battery recycling. However, these procedures can be scaled up on a pilot scale, and their profitability and environmental performance are debatable. [ABSTRACT FROM AUTHOR]

The utilization of end-of-life batteries (including Zn-C and alkaline batteries) is one of the areas that need to be perfected in order to provide environmental and human safety as well as to contribute to closing the material loop, as described in the EU Green Deal. The presented study shows the environmental impacts of the two selected pyrometallurgical technologies (processing of the black mass from waste Zn-C and alkaline batteries as an additive to an existing process of the recycling of steelmaking dust and treatment of the black mass as the primary waste material, both processes performed in a Waelz kiln). The presented LCA-based study of the recycling of end-of-life Zn-C and alkaline batteries focused on terrestrial ecotoxicity can be a useful tool in the process of the development of a circular economy in Europe, as it provides a multi-disciplinary overview of the most important environmental loads associated with the described recycling technologies. Therefore, the goal of the presented study was to compare the environmental performance (utilizing LCA) of two different metallurgical processes of black mass utilization, i.e., the conventional method utilizing black mass as a co-substrate and the newly developed method utilizing black mass as a primary substrate. [ABSTRACT FROM AUTHOR]

"Black Mass" (BM) is the industry term that indicates the powdered material recovered from the spent Li-ion batteries (LIBs) after mechanical and thermal processing to remove binder, electrolytes, plastics and steel. In addition to graphite, it contains valuable metals, including cobalt, lithium, manganese, nickel and copper. Thus, recycling and reusing BM is of paramount importance to reduce the carbon footprint of the LIB supply chain and the need for virgin materials. Capacitive deionization (CDI), which utilizes carbon-based electrodes enriched with metal oxides, is a promising and sustainable technology for brackish water desalination. This article proposes, for the first time, the reuse of BM as an electrode material for CDI of brackish water. The proposal is based on the results of a feasibility study carried out on two different grades of BM, whose physiochemical properties are investigated by a combination of analytic techniques. The evaluation of their electrochemical performance in 0.1 mol L −1 NaCl solution by cyclic voltammetry shows that, at 5 mV s −1 scan rate, electrodes prepared with as-recovered BM exhibit specific capacitance (73−87 F g −1) comparable or superior to those obtained by using virgin materials. Therefore, regardless of the details of their processing, giving a second life to BM as a CDI electrode is a viable strategy to address the needs of the circular economy and sustainability of freshwater production. [ABSTRACT FROM AUTHOR]

[Display omitted] • The presence of LFP in battery waste changes Fe and Al removal. • At pH 2 iron can be precipitated with 0.7 wt% Ni and ≤ 0.4 wt% Mn, Co, Al, and Li. • Iron precipitates as iron phosphate (FePO 4) and iron fluoride (FeF 3) • 91% of Al precipitates at pH 4.5 as AlOOH, Al-F complex keeps minor Al soluble. • Selective Fe removal or combined Fe-Al removal can be conducted with pH adjustment. There is a need to develop removal strategies for typical battery impurities–iron and aluminum–from actual hydrometallurgical recycling solutions. In this work, the investigated solution originated from lithium nickel manganese cobalt oxide (NMC) rich black mass, while iron phosphate (LFP) was used as an in situ reductant. It was found that the presence of phosphate ions supported selective iron precipitation already at pH = 2.0 (T = 60 °C, t = 3 h, NaOH), with nearly complete iron removal (97.8 %). The precipitate was rich in iron (21.5 wt%) and phosphorus (13.4 wt%); it also contained 0.7 wt% Ni and 0.3–0.4 wt% Mn, Co, Al, and Li. It is suggested that the presence of phosphate in minor amounts may cause this co-precipitation of battery metals. With the aim of combined precipitation of iron (100 %) and aluminum (91.0 %), the pH was increased up to 4.5. Although 90.8 % of fluoride precipitated, the remaining fluorides may have kept the aluminum partially in soluble form as Al-F complexes. The formed precipitate had lower iron (18.4 wt%) and phosphorus (11.4 wt%) content, whereas the impurity contents and thus the battery metals losses were slightly higher: Ni, Mn, Co, Al, and Cu were each between 1.1–1.9 wt% and Li and F < 1 wt%. In the precipitates investigated, iron was found predominantly as iron phosphate (FePO 4), whereas a minor fraction also precipitated as iron fluoride (FeF 3). The precipitated aluminum existed mainly as AlOOH. The results presented here will help to build iron and aluminum removal strategies for industrial battery recycling solutions, and also provide insights into the dominant iron and aluminum phases forming the precipitates. [ABSTRACT FROM AUTHOR]

Lithium-ion battery recycling offers an opportunity to develop innovative technologies to close the loop on the battery materials cycle and increase the resilience of the battery supply chain. Here we demonstrate a two-step pyroelectrochemical method for producing mixed-metals from lithium-ion cathodes in a molten hydroxide salt. Mixed metal oxides in the form of insoluble lithium-ion cathode materials of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and spent lithium-ion battery materials (black mass) were electrochemically reduced to a soluble form and dissolved into a molten hydroxide salt bath. Electrochemical characterization of the process salt indicated accumulation of dissolved transition metals in the salt. A separate cathode was used to produce alloys of Ni, Mn, and Co electrochemically from the dissolved lithium-ion cathode materials. Characterization by scanning electron microscopy fitted with an energy dispersive X-ray spectrometer showed transition metals present in the cathode materials were recovered at the separate cathode. This approach represents a scalable, low temperature pyroelectrochemical process that can potentially reduce the cost and close the loop of battery cathode recycling. [ABSTRACT FROM AUTHOR]

The processing and extraction of critical metals from black mass is important to battery recycling. Separation and recovery of critical metals (Co, Ni, Li, and Mn) from other metal impurities must yield purified metal salts, while avoiding substantial losses of critical metals. Solvent extraction in batch experiments were conducted using mixed metal sulphates obtained from the leach liquor obtained from spent and shredded lithium-ion batteries. Selective extraction of Mn2+, Fe3+, Al3+ and Cu2+ from simulated and real leached mixed metals solution was carried out using di-2-ethylhexylphophoric acid (D2EPHA) and Cyanex-272 at varying pH. Further experiments with the preferred extractant (D2EPHA) were performed under different conditions: changing the concentration of extractant, organic to aqueous ratio, and varying the diluents. At optimum conditions (40% v/v D2EPHA in kerosene, pH 2.5, O:A = 1:1, 25 °C, and 20 min), 85% Mn2+, 98% Al3+, 100% Fe3+, and 43% Cu2+ were extracted with losses of only trace amounts (2+, Ni2+, and Li+. The order of extraction efficiency for the diluents was found to be kerosene > Exxal-10 >>> dichloromethane (CH2Cl2) > toluene. Four stages of stripping of metals loaded on D2EPHA were performed as co-extracted metal impurities were selectively stripped, and a purified MnSO4 solution was produced. Spent extractant was regenerated after Fe3+ and Al3+ were completely stripped using 1.0 M oxalic acid (C2H2O4).

The literature indicates that utilizing pyrometallurgical methods for processing spent LiCoO2 (LCO) batteries can lead to cobalt recovery in the forms of Co3O4, CoO, and Co, while lithium can be retrieved as Li2O or Li2CO3. However, the technology’s high energy consumption has also been noted as a challenge in this recovery process. Recently, an innovative and sustainable approach using microwave (MW) radiation has been proposed as an alternative to traditional pyrometallurgical methods for treating used lithium-ion batteries (LiBs). This method aims to address the shortcomings of the conventional approach. In this study, the treatment of the black mass (BM) from spent LCO batteries is explored for the first time using MW–materials interaction under an air atmosphere. The research reveals that the process can trigger carbothermic reactions. However, MW makes the BM so reactive that it causes rapid heating of the sample in a few minutes, also posing a fire risk. This paper presents and discusses the benefits and potential hazards associated with this novel technology for the recovery of spent LCO batteries and gives information about real samples of BM. The work opens the possibility of using a microwave for raw material recovery in spent LIBs, allowing to obtain rapid and more efficient reactions.

Many countries have started their transition to a net-zero economy. Lithium-ion batteries (LIBs) play an ever-increasing role towards this transition as a rechargeable energy storage medium. Initially, LIBs were developed for consumer electronics and portable devices but have seen dramatic growth in their use in electric vehicles (EVs) and via the gradual uptake in battery energy storage systems (BESSs) over the last decade. As such, critical metals (Li, Co, Ni, and Mn) and chemicals (polymers, electrolytes, Cu, Al, PVDF, LiPF6, LiBF4, and graphite) needed for LIBs are currently in great demand and are susceptible to global supply shortages. Dramatic increases in raw material prices, coupled with predicted exponential growth in global demand (e.g., United States graphite demand from 2022 7000 t to ~145,000 t), means that LIBs will not be sustainable if only sourced from raw materials. LIBs degrade over time. When their performance can no longer meet the requirement of their intended application (e.g., EVs in the 8–12 year range), opportunities exist to extract and recover battery materials for re-use in new batteries or to supply other industrial chemical sectors. This paper compares the challenges, barriers, opportunities, and successes of the United States of America and Australia as they transition to renewable energy storage and develop a battery supply chain to support a circular economy around LIBs.

With the increasing number of electric vehicles (EVs) rises the need to recycle their used lithium-ion batteries (LIBs). During the mechanical process of the recycling of the LIB cells, a fine fraction, the so-called black mass, is created. This black mass consists mostly of the coatings originating from the cells’ electrodes and residues from the electrolyte, together with a low amount of Al and Cu from the crushed current collector foils. The amount of black mass as well as its composition is influenced by the chosen grid size at the crusher discharge. To reduce solvent emissions during the recycling process, a thermal pre-treatment can be added before crushing, which also influences the black mass and its properties due to changes in the adhesion between electrode foils and coating. This study investigates the influence of the crusher settings as well as the pre-treatment temperatures to find an optimum between the recovery of the coating and conductive salt, while limiting the amount of Al and Cu in the black mass.

Metallic contaminants pose a significant challenge to the viability of directly recycling Li-ion batteries. To date, few strategies exist to selectively remove metallic impurities from mixtures of shredded end-of-life material (black mass; BM) without concurrently damaging the structure and electrochemical performance of the target active material. We herein present tailored methods to selectively ionize two major contaminants—Al and Cu—while retaining a representative cathode (LiNi0.33Mn0.33Co0.33O2; NMC-111) intact. This BM purification process is conducted at moderate temperatures in a KOH-based solution matrix. We rationally evaluate approaches to increase both the kinetic corrosion rate and the thermodynamic solubility of Al0 and Cu0, and evaluate the impact of these treatment conditions on the structure, chemistry, and electrochemical performance of NMC. Specifically, we explore the impacts of chloride-based salts, a strong chelating agent, elevated temperature, and sonication on the rate and extent of contaminant corrosion, while concurrently evaluating the effects on NMC. The reported BM purification process is then demonstrated on samples of “simulated BM” containing a practically relevant 1 wt% concentration of Al or Cu. Increasing the kinetic energy of the purifying solution matrix through elevated temperature and sonication accelerates the corrosion of metallic Al and Cu, such that ∼100% corrosion of 75 μm Al and Cu particles is achieved within 2.5 hr. Further, we determine that effective mass transport of ionized species critically impacts the efficacy of Cu corrosion, and that saturated Cl– hinders rather than accelerates Cu corrosion by increasing solution viscosity and introducing competitive pathways for Cu surface passivation. The purification conditions do not induce bulk structural damage to NMC, and electrochemical capacity is maintained in half-cell format. Testing in full cells suggests that a limited quantity of residual surface species are present after treatment, which initially disrupt electrochemical behavior at the graphite anode but are subsequently consumed. Process demonstration on simulated BM suggests that contaminated samples—which prior to treatment show catastrophic electrochemical performance—can be recovered to pristine electrochemical capacity. The reported BM purification method offers a compelling and commercially viable solution to address contamination, particularly in the “fine” fraction of BM where contaminant sizes are on the same order of magnitude as NMC and where traditional separation approaches are unfeasible. Thus, this optimized BM purification technique offers a pathway towards viable direct recycling of BM feedstocks that would otherwise be unusable.

Hazenite (KNaMg2(PO4)2 × 14 H2O), a new type of struvite mineral, was precipitated from the potassium-rich washing water of spent alkaline battery black mass. Hazenite can be used as a fertilizer, which would be an additional benefit derived from the sustainable recovery of battery materials. Precipitation experiments were performed using different pH values (9.5–12), Mg:K:PO4 ratios ((1.0–1.5):1:(1.0–1.5)) and temperatures (10–40 °C). Based on the results, hazenite precipitated in a wide pH range under alkaline conditions. The precipitation kinetics were fast, and the purity of the hazenite was high. Overall, hazenite can be precipitated at room temperature without the addition of excess chemicals, which minimizes the consumption of chemicals and energy.

Black mass is the industry term applied to end-of-life (EoL) lithium-ion batteries that have been mechanically processed for potential use as a recycled material to recover the valuable metals present, including cobalt, lithium, manganese, nickel and copper. A significant challenge to the effective processing of black mass is the complexity of the feed material. Two samples of black mass from a European source were analysed using a combination of methods including automated SEM-EDS (AMICS) to characterise and quantify the phases present and particle chemistry. Micro X-CT imaging, overlain onto automated mineralogy images, enabled the 3D morphology of the particles to be determined. Micro-XRF was used to map the copper, nickel, manganese and cobalt-bearing phases. Since Li cannot be detected using SEM-EDS, its abundance was semi-quantified using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The integration of these complimentary analytical methods allowed for detailed phase characterisation, which may guide the potential hydrometallurgical or pyrometallurgical recycling routes and chemical assaying.

[Display omitted] • Recovery of sulfuric from leachate using solvent extraction. • Comprehensive study of the thermodynamic behavior of the leachate/tri-n-octylamine system. • Extraction of 97.6 % of the sulfuric acid under optimal conditions. • Less than 25 mg/L aluminum found in the recovered sulfuric acid. Excess sulfuric acid which is needed for the leaching process of spent lithium-ion batteries is commonly neutralized generating significant waste streams. This research aims to extract and recover sulfuric acid using tri-n-octylamine as an extraction agent. 1-octanol, 2-ethylhexanol, and tributyl phosphate are investigated as synergetic extractants and phase modifiers. An equilibrium study is carried out on both, sulfuric acid and leachate. The equilibrium constant and the stoichiometric coefficient for the overall equilibrium reaction are determined by slope analysis. The enthalpy and Gibb's enthalpy are studied by investigation of the effect of temperature. Regarding the experiments using leachate, the co-extraction of aluminum, cobalt, copper, iron, lithium, manganese, and nickel is studied, too. Moreover, the co-extraction of water is investigated as a significant increase in metal concentration in the raffinate is observed. [ABSTRACT FROM AUTHOR]

Lithium-ion batteries (LIBs) are dangerous to recycle, as they pose a fire hazard when cut and contain various chemical hazards. If recycled safely, LIBs provide a rich secondary source for metals such as lithium and cobalt, while reducing the environmental impact of end-of-life LIBs. Discharging the spent LIBs in a 5 wt.% NaCl electrolyte at room temperature enables their safe dismantling. A sludge was observed to form during the LIB discharging, with a composition of 34.9 wt.% Fe, 35 wt.% O, 17.7 wt.% Al, 6.2 wt.% C, and 4.2 wt.% Na. The average electrolytic solution composition after the first discharge cycle contained only 12.6 mg/L Fe, 4.5 mg/L Li, 2.5 mg/L Mn, and trace amounts of Ni and Co. Separating the active cathode powder from the aluminum cathode with a 10 wt.% NaOH leach produced an aqueous filtrate with an Al metal purity of 99.7%. The leach composition consisted of 9558 mg/L Al, 13 mg/L Li, 8.7 mg/L Co, and trace amounts of Mn and Ni. The hydrometallurgical sample preparation processes in this study enables the production of a pure black mass with less than 0.05 wt.% Co, 0.2 wt.% Li, 0.02 wt.% Mn, and 0.02 wt.% Ni losses from the active cathode material. [ABSTRACT FROM AUTHOR]

As battery usage increases every year, the number of spent batteries is also increasing, resulting in an important environmental issue. To examine the possibility of using the black mass (BM) obtained from spent batteries as a catalyst material for volatile organic compound (VOC) oxidation, the effect of the pretreating BM on its catalytic activity was investigated. Catalysts were prepared by pretreating the BM in three ways using water and sulfuric acid, and the catalytic performance of each catalyst was compared. The order of activity according to the pretreatment method was water and sulfuric acid hybrid pretreatment (WSBM)>sulfuric acid pretreatment (SBM)>water pretreatment (WBM)>raw (BM). The high adsorption energy site had a great influence on the activity of the catalyst. The number of acid sites and the easily movable lattice oxygen played an important role in the complete oxidation of benzene, toluene and o-xylene. At a gas hourly space velocity of 50,000 h−1, benzene, toluene, and o-xylene were removed completely on the WSBM catalyst at 370 °C, 360 °C, and 350 °C, respectively. [ABSTRACT FROM AUTHOR]

The market for lithium‐ion batteries (LIB) is experiencing substantial growth, what is owed to electromobility and the growing demand for cordless devices. Securing the raw material base for LIB is mandatory to achieve the objectives of EU commission's Green Deal. This implies not only sufficient access to lithium but also the accompanying metals, above all Co, Ni, Mn. After preceding recovery of Li2CO3 by the COOL‐Process and subsequent acid digestion of the Li‐free black mass, value metals, such as Co, Cu, Ni, and Mn were recovered by counter‐current solvent extraction. Fe (98.5 ± 0.65 %), Co/Mn (99.8 ± 0.78 %; 99.9 ± 1.11 %), Al (99.7 ± 1.07 %) and Cu/Ni (97.8 ± 1.46 %; 98.6 ± 1.32 %) were selectively extracted with high discriminatory power using cationic exchangers and solvating extractants such as D2EHPA and TBP, respectively. This way, a complete, holistic recycling process for LIB is at hand that allows for recovering housing material, lithium and the accompanying metals almost quantitatively. [ABSTRACT FROM AUTHOR]

Lithium recycling from spent LIBs along the COOL‐process produces a Li‐free metal rich black mass, which still contains the entire fraction of valuable metal such as Co, Ni, and Mn. A recycling process was developed, which allows for mobilizing these metals. The first process stage is the selective leaching of Li via COOL‐process. Subsequently, two inorganic (H2SO4 and HCl) and two organics acids (citric and gluconic acid) were tested for mobilizing the metals from the solid residue. To optimize this process stage, acid concentration as well as addition of H2O2 as a reduction reagent were investigated. The optimal conditions to dissolve valuable metals such as Co, Cu, Fe, Mn, and Ni was identified as 2 N H2SO4 and 2 vol % H2O2. [ABSTRACT FROM AUTHOR]

The utilization of end-of-life batteries (including Zn-C and alkaline batteries) is one of the areas that need to be perfected in order to provide environmental and human safety as well as to contribute to closing the material loop, as described in the EU Green Deal. The presented study shows the environmental impacts of the two selected pyrometallurgical technologies (processing of the black mass from waste Zn-C and alkaline batteries as an additive to an existing process of the recycling of steelmaking dust and treatment of the black mass as the primary waste material, both processes performed in a Waelz kiln). The presented LCA-based study of the recycling of end-of-life Zn-C and alkaline batteries focused on terrestrial ecotoxicity can be a useful tool in the process of the development of a circular economy in Europe, as it provides a multi-disciplinary overview of the most important environmental loads associated with the described recycling technologies. Therefore, the goal of the presented study was to compare the environmental performance (utilizing LCA) of two different metallurgical processes of black mass utilization, i.e., the conventional method utilizing black mass as a co-substrate and the newly developed method utilizing black mass as a primary substrate.

[Display omitted] • Black powder from NCM batteries was pyrolyzed prior to flotation. • Optimum pyrolysis conditions were determined using various surface characterizations. • Flotation of black mass successfully separated active materials. • Flotation was optimized, and the anode grade was increased via a flotation circuit. Batteries based on lithium nickel cobalt manganese oxides (NCM), which have not been extensively studied, were considered for this study. A black mass (BM) derived from a diverse mix of NCM-type batteries was pyrolyzed at three different temperatures before flotation. The optimum pyrolysis temperature was determined via X-ray spectrometry, contact angle measurements, thermogravimetry, X-ray diffraction, and X-ray photoelectron spectroscopy as 400 °C at which the active materials in the BM were successfully liberated without generating new phases on the material surfaces. This is crucial for recovering materials from the BM using flotation and their potential subsequent application in battery manufacturing, which requires high-purity materials. After optimal pretreatment, the flotation of the treated BM was conducted to separate active materials. At the laboratory scale, the optimal conditions were an impeller speed of 1600 rpm, a collector dosage of 150 g/t, a frother dosage of 150 g/t, and a pulp density of 20 g/L. Furthermore, the initial anode and cathode grades of 84 % and 92 % were further enhanced to 97 % and 95 %, respectively, by employing additional cleaning and scavenging stages. Therefore, this study offers a promising method for recovering high-purity active materials from the BM through systematic pyrolysis pretreatment and subsequent flotation. [ABSTRACT FROM AUTHOR]

The recycling of valuable metals from spent lithium-ion batteries (LIBs) is highly important to secure the sustainable production of new LIBs and reduce the dependence on virgin resources. The present paper aims to study the smelting behaviour of black mass (BM) from spent LIBs and investigate the effect of graphite on metal recovery in a carbon-saturated hot metal bath and in a low-carbon steel bath. The smelting trials of BM were conducted in a technical scale (150 kg) induction furnace using hot metal and steel scrap at operating temperatures in the range of 1278–1438 °C and 1470–1610 °C, respectively. Two grades of BM were applied in the current study; high-Ni BM and high-Co BM. Parts of both grades of the BM were briquettes to enhance the direct reduction of metal oxides with embedded graphite and to reduce the dust generation during loading into the furnace. The briquette BM was charged to carbon-saturated hot metal bath while the other part of the BM was subjected to de-coking in a muffle furnace in an oxidising atmosphere to remove graphite (37–39%) and to concentrate the valuable metals in the BM. The de-coked BM was loaded directly, without the need for the briquette, to the low-carbon steel bath. The results indicated that smelting of the de-coked BM in a steel bath is more efficient in metal recovery than the smelting of the corresponding briquette BM in a molten hot metal bath. The highest recovery rate of Co, Ni and Cu (98–99%) was obtained by smelting de-coked high-Co BM in a low-carbon molten steel bath, while the lowest recovery rate (38–55%) was obtained by smelting the briquette high-Ni BM in the carbon-saturated hot metal bath.

In order to ensure environmentally friendly mobility, electric drives are increasingly being used. As a result, the number of used lithium-ion batteries has been rising steadily for years. To ensure a closed recycling loop, these batteries must be recycled in an energy- and raw material-efficient manner. For this purpose, hydrometallurgical processes are combined with mechanical pre-treatment, including disintegration by mills, crushers and/or shears. Alternatively, electrohydraulic fragmentation (EHF) is also of great interest, as it is considered to have a selective fragmentation effect. For a better comparison, different application scenarios of EHF with other methods of mechanical process engineering for the treatment of lithium-ion batteries are investigated in the present study.