| Cite this article as: |
Juheon Lee, Kwang Won Park, Il Sohn, and Sanghoon Lee, Pyrometallurgical recycling of end-of-life lithium-ion batteries, Int. J. Miner. Metall. Mater., 31(2024), No. 7, pp.1554-1571. https://dx.doi.org/10.1007/s12613-024-2907-7
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Lithium-ion batteries (LIBs), since their commercialization by Sony in the early 1990s, have completely transformed the paradigm of energy storage technologies [1–3]. Owing to their exceptional energy density, long cycle lifespan, high charging efficiency, and lightweight characteristics, this technology has been recognized as an unparalleled energy storage solution across various industrial sectors [4–7]. In the initial stages of commercialization, portable electronic devices were the primary applications that immediately showcased the benefits of lithium-ion batteries. Devices such as laptops, smartphones, and tablets greatly benefited from the efficiency and lightness of these batteries, which facilitated reductions in device thickness and extensions in usage time [8]. Subsequently, with the rapid growth of the electric vehicle (EV) and plug-in hybrid vehicle (PHEV) industries, lithium-ion batteries quickly established themselves as the core energy storage medium in that domain. Especially, as the significance of electric vehicles grow with global pressures for carbon emission reductions and the increasing demand for environmentally friendly transportation, the importance of lithium-ion batteries are concurrently emphasized [9–11].
The expansion of renewable energy usage has further highlighted the need for large-scale energy storage linked to the stabilization of the power grid. Renewable energy sources, such as wind and solar, have inconsistent production levels. As a result, lithium-ion batteries have played a significant role in balancing the production and consumption of such energies [12–14]. Furthermore, there has been a growing use of lithium-ion batteries in cutting-edge technological areas that require diverse energy storage solutions, such as unmanned aerial vehicles, drones, and smart grids [15–17]. Concurrently, research is vigorously underway to improve battery performance, enhance safety, and reduce production costs, with continuous exploration of potential applications in a range of industrial sectors [18–20].
The extensive growth of lithium-ion batteries in a wide range of applications has, as expected, led to a rapid increase in demand for the batteries. According to several recent papers and reports from specialized market research firms [21–22], the demand for lithium-ion batteries is projected to surpass an annual compound growth rate of 20% by 2030 (Fig. 1(a)), with the expansion of applications in electric vehicles and large-scale energy storage solutions being the primary drivers of this growth.
Recently, this heightened demand for batteries is introducing complexities in the supply chain for essential raw materials like lithium, nickel, cobalt, manganese, and aluminum [23]. These materials have a decisive impact on the core performance characteristics and efficiency of battery cells. Especially lithium, due to its geographical distribution and mining restrictions, is increasing the geopolitical risk factors associated with its supply [24]. Nickel, as a fundamental element for enhancing energy density, is seeing its demand surge rapidly. Meanwhile, cobalt, primarily mined in regions with high political instability, faces substantial price and supply fluctuations. Furthermore, manganese and aluminum, crucial in ensuring the electrochemical stability and lifespan of batteries, highlight the importance of sustainable supply strategies for these materials [25].
Additionally, the rise in battery applications is leading to an increase in the generation of spent LIBs [26–27]. This presents new environmental responsibilities and opportunities, as the global market for recycling and disposal of spent LIB is on a consistent upward trajectory (Fig. 1(b)). Currently, the research and development of spent LIB recycling technologies are emerging as important topics from the perspectives of environmental sustainability and resource optimization. Experts anticipate that this spent LIB market will grow rapidly in the future, and it will be regarded as a crucial business sector and central element for environmental protection within the industrial ecosystem.
A key solution to these problems is the effective recycling of spent lithium-ion batteries. By recycling, we can recover valuable elements like lithium, cobalt, nickel, and other precious metals from batteries, alleviating resource scarcity issues and reducing environmental burdens. Moreover, recycling proves to be more efficient than mining new resources, offering a sustainable economic advantage [28–30]. Consequently, the research and development of lithium-ion battery recycling technologies are of paramount importance currently.
The growing interest in recycling lithium-ion batteries has led to a surge in research and development activities, exploring various technical approaches. Among them, hydrometallurgy boasts advantages such as operating at relatively low temperatures and the ability to extract metals of high purity [31–34]. Also, if solutions that minimize environmental impacts are used, it can also offer environmental benefits [35]. However, such methods require significant facility investments and high operational costs [31]. They also come with drawbacks like the complexity of the treatment process, the generation of large amounts of liquid waste, and limited recovery rates of specific metals [36]. Biometallurgical recycling is a technique for extracting metals in an environmentally friendly manner. It uses specialized microorganisms to enhance energy efficiency and effectively interact with minerals [37–40]. Yet, this method has limitations such as extended metal recovery times and the necessity for specific environmental conditions to activate the microorganisms [41–43]. The pyrometallurgical recycling discussed in this research offers significant advantages in efficiently processing large quantities of batteries [44–46]. It also possesses flexibility in processing various types of batteries without the need for individual sorting, allowing direct treatment without battery discharge and disassembly [47]. However, while the process doesn’t produce wastewater, it carries the risk of emitting harmful gases and consumes a substantial amount of energy [48–50]. Especially, the inability to effectively recover lithium and other valuable metals has been a significant drawback of pyrometallurgical recycling [27,46,51–52] making hydrometallurgical recycling the more dominant method for a time. However, with the development of innovative technologies that address these shortcomings [53–56] and more importantly, given the rapidly increasing volume of spent batteries, pyrometallurgical recycling is gaining attention as the most suitable solution for the demands of the burgeoning spent battery market. Furthermore, as batteries evolve with increasingly diverse compositions, the ability to process them flexibly and in an integrated manner makes pyrometallurgical recycling unparalleled compared to other recycling technologies. However, in order to fully harness the potential of pyrometallurgical recycling, systematic and in-depth research is still necessary.
This review is part of such efforts, aiming to present the overall research trends and developments in spent battery recycling centered around pyrometallurgical recycling. Based on the latest research results, we will discuss optimization strategies for the pyrometallurgical recycling process, as well as the integration status with other recycling technologies. Furthermore, we will explore the technical characteristics based on fundamental issues of the thermal treatment process, especially its environmental aspects such as energy efficiency and hazardous substance emissions. Alongside this, by referencing actual commercialization cases in various countries, we will verify the practicality and market value of the pyrometallurgy process. The prospects of pyrometallurgical recycling technology will also be thoroughly discussed.
In conclusion, this paper intends to present the position of pyrometallurgical recycling in the spent battery recycling sector and offer a vision for the future of this technology. By distinguishing it from traditional recycling methodologies, we will provide a strategic viewpoint on how the pyrometallurgical recycling can potentially pave the way for a sustainable future.
Pyrometallurgy encompasses a wide range of scientific and technological practices that leverage the chemical and physical transformations of both metallic and non-metallic materials under high-temperature conditions [57–59]. The fundamental process flow of the spent LIBs recycling depicted in Fig. 2 initiates at the preprocessing stage and progresses through multiple stages until reaching the final products. Each stage is meticulously adjusted to optimize the recovery of lithium and valuable metals. In pyrometallurgical recycling process, the pretreatment stage can be omitted if not necessary. Additionally, smelting is frequently integrated with hydrometallurgical methods to enhance efficiency and recovery rates. It’s also worth noting that alternative processes (Fig. 3) based on roasting can be employed instead of smelting. This paper reviews the latest research findings at each stage of the pyrometallurgical recycling process, aiming to assess the current state of pyrometallurgical recycling technology and explore future research directions and potential improvements.
The pretreatment in recycling spent lithium-ion batteries encompass the dismantling of the battery casing and the subsequent separation of internal components such as the cathode, anode, and separators. This intricate process is sequentially structured and typically includes stages like discharge, disassembly, mechanical treatment, sieving, separation, dissolution, and thermal treatment [61]. In the realm of pyrometallurgical recycling, a distinguishing advantage is that many of these preprocessing steps can be significantly simplified or even bypassed entirely. This facilitates the direct treatment of discarded batteries. Nonetheless, depending on specific circumstances and to ensure optimal process stability and efficiency, some preprocessing stages might still be incorporated. Alternatively, certain treatments might be appended to the tail end of the recycling process to enhance or complement the overall performance of the pyrometallurgical recycling methodology.
Before disassembling a battery, it is essential to perform a discharge treatment on the remaining capacity of LIBs. This is because if the anode and cathode of a LIB with residual capacity come into contact, there’s a risk of short-circuiting or spontaneous ignition [36]. Various discharge tests have been conducted using solutions like water, NaCl, NaSO4, FeSO4, ZnSO4, KCl, NaNO3, MnSO4, MgSO4, and others [62–65]. Among them, discharge curves for each type of aqueous solution concentration, as shown in Fig. 4, indicate that the NaCl solution demonstrated the fastest discharge rate. At a 20wt% concentration, complete discharge was achieved in just 4.4 h. However, there are issues with chlorine gas production and galvanic corrosion of the Fe shell when using NaCl [62]. To address these challenges and maximize discharge efficiency, factors such as the battery’s state of charge (SoC), salinity concentration, stirring conditions of the solution, and temperature were studied. Based on these results, discharge techniques using NaCl continue to be the most commonly utilized method to date.
The disassembly process can vary in depth, from breaking down battery packs into modules or cells, or further disassembling cells into electrodes. The depth of disassembly can affect the quality and efficiency of the recovery. While it’s possible to disassemble manually, research has found more efficient methods. For instance, when targeting pouch-type batteries that have electrode–separator assemblies stacked in a Z-folding manner, a system was designed with three modules, as illustrated in Fig. 5. The resulting prototype confirmed that this approach was faster, safer, and more economical [66]. However, the commercialization of automated disassembly concepts remains limited. The diversity in design and structure of battery packs poses challenges to the design and validation of automated disassembly processes [67].
Mechanical treatment involves various equipment such as impact, electric, slow-speed, and high-speed systems and can be carried out in wet or dry conditions [68–70]. After this grinding process, the resulting diverse products are physically separated to produce a black mass concentrated with valuable metals [71]. Through this method, the efficiency of the solvent extraction process can be enhanced, which is the leaching of electrode active materials. Furthermore, the energy consumption of subsequent processes can be reduced [72].
Planetary ball mill is primarily used in mineral recycling technology, but when applied to mechanochemical reduction technology in lithium-ion battery recycling, it has shown improved extraction results for lithium and cobalt [60]. However, Dry crushing can pose safety issues or subsequent process efficiency problems depending on the method of crushing, such as the generation of organic compounds, corrosion of the battery casing, and over-grinding of electrode active materials [73]. As a countermeasure, the temperature of the grinder tank is reduced to an ultra-low 77 K to diminish the reactivity of lithium during grinding. Alternatively, recent methods grind in a gaseous atmosphere using gases like Ar, N2, or CO2 to eliminate hazardous factors [74].
Grinding flotation [75] is a physical separation method that utilizes the structural characteristics of LiCoO2 and graphite. Based on the concentration results of LiCoO2 as shown in Fig. 6, with respect to the grinding time, the optimal condition was identified after grinding for 5 min. Under this condition, the concentration of LiCoO2 and graphite were 97.19wt% and 82.57wt%, respectively, and their recovery rates were 49.32% and 73.56%, respectively. Additionally, the surface morphology and elemental distribution of electrode particles before and after grinding were systematically analyzed to elucidate the dry modification mechanism. In the case of graphite, it is crushed by horizontal shear force (F1) and vertical rolling pressure (F2). Conversely, LiCoO2 is also crushed by horizontal shear force (F′1) and vertical rolling pressure (F′2), but its higher strength leads to the occurrence of smoothing attributed to wear. Wet grinding has the advantage of suppressing dust and absorbing the heat generated during grinding, preventing issues like high temperatures or explosions. However, one must consider the downside that during the grinding process, battery binders, electrolytes, and other toxic substances may leach into the solution, forming wastewater, leading to additional wastewater treatment costs.
Sieving refers to the process of sorting crushed battery fragments based on their sizes in order to differentiate between the cathode materials and the current collectors. For this classification, a variety of equipment is utilized, including vibrating screen, rotary screens, air screens, and magnetic screens. The sorting efficiency is influenced by several factors, such as the crushed fragment size, mesh dimensions, vibration frequency, and magnetic force strength. As a result, both experimental and numerical methods are deployed to identify the optimal sorting conditions. Generally, in the larger size ranges, materials like aluminum and copper are predominantly found. Conversely, as the particle size becomes smaller, electrode materials such as cobalt and graphite become more prevalent [76]. Recently, new classification tools have been developed, including magnetic induction screens, optical screens, electrostatic screens, and acoustic screens. These are designed to leverage the unique characteristics of electrode active materials, enabling more precise and faster sorting. As illustrated in Fig. 7 [77], when applying electrostatic separation to spent lithium-ion batteries processed to sizes greater than 5 mm via a hammer mill, if optimized conditions are used (specifically, a roll rotation speed of 20 r⋅min−1, an electrode voltage of 25 kV, an electrostatic electrode distance of 6 cm, and a deflector inclination angle of 0°), it’s possible to obtain a conductive powder containing 98 wt% of metal materials and a non-conductive powder containing 99.6 wt% of polymers. Depending on the battery model, these can further be separated into metal content ranging from 25.08wt%–47.59wt%, polymers between 2.87wt%–7.71wt%, LiCoO2 and graphite in the range of 25.97wt%–39.92wt%, and a mixture comprising 4.5wt%–5.46wt%.
Separation techniques are essential tools in the recycling process, particularly when it comes to distinguishing between various electrode materials based on their inherent physical properties. These methods play a pivotal role in enhancing the purification and recovery of materials, especially when certain residues remain even after mechanical treatment and sieving operations.
Among the wide array of separation methods, magnetic separation capitalizes on the inherent ferromagnetic nature of certain materials, like iron. This method involves utilizing magnets, and the efficiency of this separation is contingent upon the magnet’s strength and its proximity to the materials. This makes optimizing the magnetic field imperative for the effective extraction of magnetic substances.
On the other hand, density separation exploits the varied densities of materials. By leveraging either gravity or centrifugal force, materials can be systematically segregated. Crucial to this method’s effectiveness is the precise control over the solution’s viscosity and density parameters.
Froth flotation is another distinct method, wherein selective chemicals are introduced to generate bubbles on the surface of a liquid medium. Depending on the affinity of materials to these bubbles, they either rise (buoy) or settle (sediment), enabling an effective separation. The chemical type and its concentration play a vital role in this method’s efficacy.
A method that takes advantage of electrical properties, both static and induced, allows for the selective separation of materials based on their conductive or dielectric nature. Parameters like voltage and frequency play an instrumental role in dictating the separation efficiency in this method [78–81].
Given that each material responds uniquely to these separation methods, extensive experimental endeavors are required to fine-tune and optimize each approach for specific applications. Among these techniques, eddy current separation (ECS) is emerging as a particularly eco-friendly alternative. It’s designed for the segregation of non-ferrous metal particles, specifically those within the 2 to 10 mm size range, without generating any waste byproducts [81]. Highlighted in the research mentioned, there was an evident challenge with ECS’s performance for non-ferrous metals during LiFePO4 (LFP) processing. However, through an iterative methodology and enhanced modeling precision, a significant breakthrough was achieved. The results showcased the successful separation of copper and aluminum foils, attained at a roller speed of 800 r⋅min−1, with a distinction in particle size ratio reaching up to 1.72.
Dissolution is a critical step aimed at eliminating the residual binder and Al foil that persist after the initial pretreatment. Its primary objective is to ensure the comprehensive recovery of the remaining cathode materials. To achieve this, a solvent treatment is deployed to dissolve and subsequently detach the binder and Al foil.
There are some solvents that have been tested for this specific purpose. Among them, NMP (N-Methyl-2-pyrrolidone), DMAC (Dimethylacetamide), DMF (Dimethylformamide), DMSO (Dimethyl sulfoxide), and ethanol stand out. Intriguingly, when ultrasonic treatment was incorporated with these solvents, NMP emerged as the most effective solvent with a dissolution rate of an impressive 99% [82]. This led to a deeper investigation, graphically represented in Fig. 8, that evaluated the various factors affecting the ultrasonic cleaning process using NMP. Through rigorous experimentation, it was determined that an optimal combination of a temperature setting of 70°C, an ultrasonic power output of 240 W, and a time duration of 90 min yielded the best results. Under this configuration, the separation efficiency of the cathode material was observed to surpass 99%, showcasing the effectiveness of the process [83]. Furthermore, continued research has been conducted using molten salt [84], and alkaline solutions [85–86] to dissolve and separate the Al current collector.
Thermal treatment methods for lithium-ion batteries encompass incineration and pyrolysis. Both induce thermodynamic conversions, specifically designed to safely break down the organic binders and flammable electrolytes found within lithium-ion batteries.
Incineration involves combustion in the presence of oxygen. This method subjects the material to high temperatures in an oxygen-rich environment, enabling the complete oxidation and breakdown of organic constituents. On the other hand, pyrolysis is a heat treatment process conducted in the absence of air or oxygen. This oxygen-deprived environment ensures that materials are thermally decomposed rather than combusted.
The removal of organic binders and carbon plays a pivotal role, as these components significantly influence the recovery rates of lithium and cathode materials. Through incineration at 700°C, there has been documented evidence of improved recovery rates of cobalt and lithium due to the reduction of LiCoO2 and the removal of carbon [87]. During pyrolysis, in an anoxic condition, LiCoO2 undergoes decomposition at 600°C to form Li2O and CoO. When temperatures exceed 800°C, the resultant products are Li2CO3 and metallic Co. During this process, organic binders like PVDF undergo thermal degradation at approximately 350°C [88]. The presence of oxygen, interestingly, tends to lower the activation energy required for thermal decomposition. As such, decomposition temperatures in an oxygen atmosphere were recorded at around 320°C, while in a nitrogen atmosphere, the decomposition temperature rose to about 450°C [89]. Other organic components, such as conductive carbon and acetylene black, commence decomposition at temperatures above 600°C [90].
It’s essential to highlight that during the incineration process, the emission levels of detrimental gases, like HF (hydrogen fluoride) or monomer vinylidene fluoride (VDF), along with carbon monoxide and carbon dioxide, tend to be significantly higher compared to the pyrolysis process. This underlines the necessity for implementing rigorous management and control measures during the incineration process to ensure environmental safety and sustainability.
In pyrometallurgy, the roasting process plays a crucial role. The roasting process is used to thermally decompose the cathode active materials of spent lithium-ion batteries, such as LiCoO2, LiCoNiO2, and LiNiMnCoO2, at high temperatures to separate lithium and cobalt. The reaction mechanism for recovering lithium and cobalt from the LiCoO2 cathode material using Carbothermic reduction (CTR) roasting has been proposed through various studies based on thermodynamic approaches [53,91]. These reaction mechanisms have led to fundamental research in the pyrometallurgical recycling process of sustainable lithium-ion batteries. A thermochemical study on the reduction reaction of LiCoO2, using an isothermal method for kinetic analysis, confirmed a single-step rate-determining mechanism with an activation energy of 165.8 kJ⋅mol−1 within the suggested optimal temperature range of 880–1200°C [56]. Another study [92] assessed the kinetics of isothermal reduction of LiCoO2 from 700–1100°C. In the early stage, the reduction of LiCoO2 follows a diffusion-controlled mechanism, and the Ginstling–Brounshtein model was used to verify an activation energy of 121 kJ⋅mol−1. In the later stage, it is controlled by the nucleation of Co, with the activation energy calculated to be 95 kJ⋅mol−1. Such kinetic studies can assist in designing process parameters (temperature, reaction time, carbon equivalent, etc.) to obtain specific recovery products of lithium and cobalt. In practice, after CRT roasting at 750°C for 60 min with a 15wt% carbon equivalent, the recovery of lithium yielded a purity of 99.55wt% Li2CO3 with a recovery rate of 99.10% [93].
Direct reduction of Co3O4 with C, \Delta {G}^{\ominus } represents standard gibbs free energy, T represents temperature.
| \begin{aligned}[b] &2\mathrm{C}{\mathrm{o}}_{3}{\mathrm{O}}_{4}+\mathrm{C}\left(\mathrm{s}\right)\to6\mathrm{C}\mathrm{o}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right),\\ & \quad \Delta {G}^{\ominus }=-65105-344.1T\end{aligned} | (1) |
Direct reduction of LiCoO2 with C:
| \begin{aligned}[b] &4\mathrm{L}\mathrm{i}\mathrm{C}\mathrm{o}{\mathrm{O}}_{2}\left(\mathrm{s}\right)+\mathrm{C}\left(\mathrm{s}\right)\to2\mathrm{L}{\mathrm{i}}_{2}\mathrm{O}\left(\mathrm{s}\right)+4\mathrm{C}\mathrm{o}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right),\\ &\quad \mathrm{ }\Delta {G}^{\ominus }=160726-315.8T\end{aligned} | (2) |
Thermal decomposition of Li2CO3:
| \begin{aligned}[b] & \mathrm{L}\mathrm{i}_2\mathrm{C}\mathrm{O}_3\left(\mathrm{s}\right)\to\mathrm{L}\mathrm{i}_2\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}\mathrm{O}_2\left(\mathrm{g}\right), \\ & \quad \mathrm{ }\Delta G^{\ominus}=179092-150.4T\;(T < 720^{\circ}\mathrm{C})\end{aligned} | (3) |
| \begin{aligned}[b]& \mathrm{L}{\mathrm{i}}_{2}\mathrm{C}{\mathrm{O}}_{3}\left(\mathrm{l}\right)\to \mathrm{L}{\mathrm{i}}_{2}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right),\\ &\quad \mathrm{ }\Delta {G}^{\ominus }=129832-79.7T\;(T\ge 720^{\circ}\mathrm{C})\end{aligned} | (4) |
Boudouard reaction:
| \mathrm{C}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right)\to 2\mathrm{C}\mathrm{O}\left(\mathrm{g}\right),\;\Delta {G}^{\ominus }=123299-175.1T | (5) |
Direct and indirect reduction of CoO:
| \begin{aligned}[b] & \mathrm{C}\mathrm{o}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}\left(\mathrm{s}\right)\to \mathrm{C}\mathrm{o}\left(\mathrm{s}\right)+\mathrm{C}\mathrm{O}\left(\mathrm{g}\right),\\ & \quad \mathrm{ }\Delta {G}^{\ominus }=79347-158.9T \end{aligned} | (6) |
| \begin{aligned}[b] & \mathrm{C}\mathrm{o}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}\mathrm{O}\left(\mathrm{g}\right)\to \mathrm{C}\mathrm{o}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right),\\ & \quad \mathrm{ }\Delta {G}^{\ominus }=-43952-16.2T\end{aligned} | (7) |
Using a similar method, based on the reaction mechanism for the carbothermic reduction of LiNiMnCoO2, roasting at 550 and 650°C for 30 min resulted in recovery rates of Li, Ni, Co, and Mn all exceeding 90%. In this case, Li was recovered through the water leaching of Li2CO3, while the remaining Ni, Co, and Mn were recovered through acid leaching [94–95].
Thermal decomposition for LiNi1/3Co1/3Mn1/3O2:
| \begin{aligned}[b] &12\mathrm{L}\mathrm{i}{\mathrm{N}\mathrm{i}}_{1/3}{\mathrm{C}\mathrm{o}}_{1/3}{\mathrm{M}\mathrm{n}}_{1/3}{\mathrm{O}}_{2} \to 6{\mathrm{L}\mathrm{i}}_{2}\mathrm{O}\left(\mathrm{s}\right)+4\mathrm{N}\mathrm{i}\mathrm{O}\left(\mathrm{s}\right)+\\ & \quad 4\mathrm{C}\mathrm{o}\mathrm{O}\left(\mathrm{s}\right)+4\mathrm{M}\mathrm{n}{\mathrm{O}}_{2}\left(\mathrm{s}\right)+{\mathrm{O}}_{2}\left(\mathrm{g}\right)\end{aligned} | (8) |
Carbothermic reduction of nicke, cobalt, and manganese oxides:
| 2\mathrm{N}\mathrm{i}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}\left(\mathrm{s}\right)\to 2\mathrm{N}\mathrm{i}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right) | (9) |
| 2\mathrm{C}\mathrm{o}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}\left(\mathrm{s}\right)\to 2\mathrm{C}\mathrm{o}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right) | (10) |
| 2{\mathrm{M}\mathrm{n}\mathrm{O}}_{2}\left(\mathrm{s}\right)+\mathrm{C}\left(\mathrm{s}\right)\to 2\mathrm{M}\mathrm{n}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right) | (11) |
Boudouard reaction:
| 2\mathrm{C}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right)\to 2\mathrm{C}\mathrm{O}\left(\mathrm{g}\right) | (12) |
The overall reaction of reduction roasting for LiNi1/3Co1/3Mn1/3O2:
| \begin{aligned}[b]&12\mathrm{L}\mathrm{i}{\mathrm{N}\mathrm{i}}_{1/3}{\mathrm{C}\mathrm{o}}_{1/3}{\mathrm{M}\mathrm{n}}_{1/3}{\mathrm{O}}_{2}+\mathrm{C}\left(\mathrm{s}\right)\to 6{\mathrm{L}\mathrm{i}}_{2}\mathrm{C}{\mathrm{O}}_{3}\left(\mathrm{s}\right)+\\ &\quad 4\mathrm{N}\mathrm{i}\left(\mathrm{s}\right)+4\mathrm{C}\mathrm{o}\left(\mathrm{s}\right)+4\mathrm{M}\mathrm{n}\mathrm{O}\left(\mathrm{s}\right)+\mathrm{C}{\mathrm{O}}_{2}\left(\mathrm{g}\right) \end{aligned} | (13) |
The advantages of such roasting processes are that they can react quickly at high temperatures, and they have high recovery rates for cobalt and nickel. However, a drawback of the actual CRT roasting process is that during water leaching, the solubility of lithium from Li2CO3 (12.9 mg∙mL−1 [96]) is low, making the recovery inefficient, and there’s a significant energy consumption in evaporative crystallization.
To enhance the efficiency of lithium recovery, additional processes have been proposed. These include chlorination, sulfation, and nitration roasting. In chlorination, NH4Cl is used as a reducing agent to produce LiCl. For sulfation, SO2 or Na2SO4 is employed to generate Li2SO4. In nitration, HNO3 is utilized to yield LiNO3 [85,97–99] All these compounds have high solubility in water, making them conducive for lithium recovery [100–102].
Chlorination roasting reaction of LiCoO2:
| \begin{aligned}[b]&2\mathrm{L}\mathrm{i}\mathrm{C}\mathrm{o}{\mathrm{O}}_{2}\left(\mathrm{s}\right) +8\mathrm{H}\mathrm{C}\mathrm{l}\left(\mathrm{g}\right)\to 2\mathrm{L}\mathrm{i}\mathrm{C}\mathrm{l}\left(\mathrm{s}\right)+\\ &\quad 2\mathrm{C}\mathrm{o}{\mathrm{C}\mathrm{l}}_{2}\left(\mathrm{s}\right)+{\mathrm{C}\mathrm{l}}_{2}\left(\mathrm{g}\right)+{4\mathrm{H}}_{2}\mathrm{O}\left(\mathrm{g}\right) \end{aligned} | (14) |
Sulfation roasting reaction of LiCoO2:
| \begin{aligned}[b]&8\mathrm{L}\mathrm{i}\mathrm{C}\mathrm{o}{\mathrm{O}}_{2}\left(\mathrm{s}\right)+6\mathrm{S}{\mathrm{O}}_{2}\left(\mathrm{g}\right)+{\mathrm{O}}_{2}\left(\mathrm{g}\right)\to 2\mathrm{L}{\mathrm{i}}_{2}\mathrm{S}{\mathrm{O}}_{4}\left(\mathrm{s}\right)+\\ &\quad 2\mathrm{L}{\mathrm{i}}_{2}\mathrm{C}\mathrm{o}(\mathrm{S}{\mathrm{O}}_{4}{)}_{2}\left(\mathrm{s}\right)+6\mathrm{C}\mathrm{o}\mathrm{O}(\mathrm{s}) \end{aligned} | (15) |
Nitration roasting reaction of LiCoO2:
| \begin{aligned}[b] &\mathrm{L}\mathrm{i}\mathrm{C}\mathrm{o}{\mathrm{O}}_{2}\left(\mathrm{s}\right)+4\mathrm{H}\mathrm{N}{\mathrm{O}}_{3}\left(\mathrm{a}\mathrm{q}\right)\to\mathrm{L}\mathrm{i}\mathrm{N}{\mathrm{O}}_{3}\left(\mathrm{s}\right)+\\ &\quad \mathrm{C}\mathrm{o}(\mathrm{N}{\mathrm{O}}_{3}{)}_{2}\left(\mathrm{s}\right) +\mathrm{N}\mathrm{O}\left(\mathrm{g}\right)+{\mathrm{O}}_{2}\left(\mathrm{g}\right)+{2\mathrm{H}}_{2}\mathrm{O}(\mathrm{g})\end{aligned} | (16) |
In the case of chlorination roasting, a high metal recovery rate of over 97% was observed, along with the removal of impurities like Al, P, and F in the form of precipitates such as AlPO4 and AlF3 [97]. When sulfidation roasting was conducted at 700°C under a gas atmosphere of 10vol%SO2–1vol%O2–89vol%Ar, followed by water leaching, a thermodynamically unexpected Li2Co(SO4)2 was formed. As a result, only 17.4% of Co was extracted, indicating the need for further research [98].
Smelting is a metallurgical process specifically designed for the recovery of metals from spent lithium-ion batteries by melting them at temperatures surpassing their melting points. The process is primarily carried out in electric furnaces and proceeds in two distinct stages [45]. The first stage involves heating at a low temperature to induce the evaporation of the electrolyte and prevent explosions. Subsequently, in the second stage, the material is melted at a high temperature. At this point, all organic matter is burned and used as energy, producing metal alloys and slag as by-products. This metal alloy contains elements like cobalt, nickel, copper, and aluminum, while the slag contains lithium, manganese, and iron. Although smelting has the advantage of being a simple and fast process, it has a critical drawback in that it is challenging to recover the lithium and manganese that end up in the slag.
Therefore, slag design technology is essential to overcome these shortcomings and optimize the process [103]. Slag systems like CaO–SiO2–Al2O3 [104], FeO–SiO2–Al2O3 [105], and MnO–SiO2–Al2O3 [106] are primarily used. In a metal/slag system, the distribution ratio of valuable metals between the alloy and slag is determined by the composition of the slag, oxygen partial pressure, temperature, etc., which is linked to the recovery rate of the valuable metals [107]. As shown in Fig. 9, in the CaO–SiO2–Al2O3 slag system, when the w(CaO)/w(SiO2) ratio is 1.0, the activity coefficient (γ) values of NiO and CoO in the slag are maximized, improving the recycling efficiency of nickel and cobalt [104]. Subsequently, valuable metals are recovered from the alloy through hydrometallurgy [108–110]. Although lithium recovery from slag has been known to be challenging, research is underway using additives like CaCl2 for chlorination roasting, vaporizing the lithium as LiCl [51,111–113]. Recently, as shown in Fig. 10, by reacting Li-bearing materials under an Ar atmosphere at 1100°C for 18 h, a recovery rate of 90% from LIB slag was achieved, with a LiCl purity of 90wt% confirmed [113]. Additionally, as known from non-ferrous and steel smelting sectors, high-temperature physicochemical properties of slag, such as viscosity [114], foaming[115], and MgO solubility [116] are essential considerations for operational optimization. Research considering these aspects for recycling lithium-ion battery slag is also underway [117].
Various pyrometallurgical recycling processes have been commercialized in countries around the world, each with distinct features in terms of scale, technology, and products. Among the leading companies that handle over 5000 t⋅a−1, as summarized in Table 1, are Umicore, Glencore, Inmetco, Accurec, and JX Nippon Mining and Metals.
| Company | Capacity / (t⋅a−1) | Products | Li recovery | Ref |
| Umicore | Ni, Co, Cu, Fe, CoCl2, Ni(OH)2 | Loss | [118–119] | |
| Glencore | Co–Ni–Cu alloy | Loss | [118,120] | |
| Inmetco | Co–Ni–Fe alloy | Loss | [51,121] | |
| Accurec | Co–Ni–Mn–Fe alloy Li3CO3 | 50% | [51,118] | |
| JX Nippon Mining and Metals | Ni, Co, Li2CO3, MnCO3 | 70% | [122] |
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The Umicore recycling process is a hybrid of pyrometallurgy and hydrometallurgy [118] capable of treating all types and sizes of lithium-ion batteries with a capacity of 7000 t⋅a−1. Batteries with metal or plastic casings removed are melted directly in a shaft furnace at ultra-high temperatures (UHT) exceeding 3000°C, making the process very straightforward and efficient [119]. A metal alloy of valuable metals (Co, Cu, Ni, Fe) is obtained, followed by acid leaching with HCl and solvent extraction in hydrometallurgy, recovering over 95% of the valuable metals in forms like Cu, Fe, CoCl2, and Ni(OH)2 [118]. However, a significant amount of Li is lost as dust. To recover Li from slag requires complicated hydrometallurgical process and significant costs. As a result, Umicore sells the slag as aggregate for concrete to construction companies. Yet, Umicore aims to develop a completely closed-loop lithium-ion battery recycling process [119].
The Glencore recycling process, like Umicore, treats 7000 t of batteries annually, combining pyrometallurgy and hydrometallurgy. After discharging and disassembling at the cell level, it is processed at 1300°C in a rotary kiln. Cobalt is recovered through hydrometallurgy of the matte. Originally designed for processing Co, Ni, and Cu ores, most of the remaining materials are consumed as heat sources or reducing agents, and lithium is lost as slag [118,120].
The Inmetco process recovers nickel, cobalt, and iron, producing alloy steel. Initially designed to process by-products like flue dust, mill scale, and swarf from stainless steel production, it now processes 6000 t of waste batteries annually. It’s heat-treated at 1260°C for 20 min using carbon and organics as reducing agents and subsequently refined in another furnace [121]. Other than iron, nickel, and cobalt recovered as alloy, lithium is lost as slag [51].
Accurec combines mechanical processing, high-temperature melting, and water treatment to recycle all types of lithium-ion batteries [118]. After removing the electrolyte at 250°C through a thermal decomposition process, the cathode material is separated through multiple physical steps [51]. Co–Ni–Mn–Fe alloy and lithium in the form of Li2CO3 are recovered from the separated cathode material through a vacuum thermal decomposition process.
Lastly, the JX Nippon Mining and Metals recycling process combines pyrometallurgy and hydrometallurgy. Initially, it only processed waste cathode material, but it later transitioned to handle end of life (EOL) lithium-ion batteries [122]. Incineration evaporates organic materials, electrolytes, and other harmful solvents, followed by mechanical sorting. The primarily cathode-composed fines undergo leaching, solvent extraction, and electrolysis in hydrometallurgy to produce electrolytic Ni and Co as main products, and Li and Mn carbonates are recovered as by-products through a precipitation process.
The increase in the use and production of lithium-ion batteries (LIBs) has led to active discussions globally regarding regulations and policies related to lithium-ion batteries. While direct content on battery recycling technology is still scant, recent studies emphasize the importance of related regulations and policies, analyzing their impact [123–126]. Fig. 11 compares the 2020 EU (European Union) lithium-ion battery regulations to their 2006 version, highlighting changes such as mandatory recycling material use, material-specific recycling efficiencies, and battery passports among circular economy requirements, introducing new regulations previously unseen [127–128].
These regulatory changes in the EU, directly applicable to the European market, will indirectly affect the global landscape due to the international nature of the LIB supply and value chain [128]. Not only in the EU but also in major markets including China and the US, battery-related laws focus on environmental protection and human health, contributing to the promotion of waste battery recycling and the maturity of recycling technologies [126,128]. However, except for China, policies specifically regarding waste battery recycling technology are yet to be properly established. China has set direct standards for recycling enterprises, including location, technology and equipment, energy efficiency, environmental protection, and safe production, making its policies more concrete in this field [126]. These policies and regulations significantly influence the maturity and future direction of waste battery recycling technology, hence the urgent need for their establishment.
From a pyrometallurgical recycling perspective, current mandatory recycling material use regulations are expected to increase the overall volume of battery recycling, positively impacting the industry. However, regulations like material recovery targets demand technological innovation to overcome limitations in material recovery within pyrometallurgical recycling processes. Especially considering life cycle assessments (LCAs) of existing pyrometallurgical recycling technologies from previous studies [44], regulations such as mandatory carbon footprint reporting could critically affect the currently commercialized pyrometallurgical recycling processes, underscoring the immediate need for the development of low-carbon pyrometallurgical recycling process technologies.
Economic analysis of spent battery recycling processes provides critical information for companies making decisions about entering or expanding in the market at the early stages of growth in the spent battery recycling sector. Such analysis not only influences the formation of business models but also plays a vital role academically by highlighting the need for technological innovation in specific recycling technology areas and suggesting future research directions.
A study analyzing the profitability of different battery types in the pyrometallurgical recycling process [129] found that only LiNi0.33Mn0.33Co0.33O2 (NMC333) was profitable among NMC333, LiNi0.8Mn0.1Co0.1O2 (NMC811), LFP, and LiMn2O4 (LMO). Although the study anticipates improved profitability with scale expansion, it does not account for the logistics cost of spent batteries and the cost of CO2 emissions, making accurate predictions challenging. However, what is clear is that the current commercial stage pyrometallurgical recycling process is limited in lithium recovery, thus heavily reliant on the content of nickel and cobalt, emphasizing the need for technological innovation in lithium recovery within pyrometallurgical recycling processes.
Another study [108] conducted an economic analysis applying a customized EverBatt model to pyrometallurgy and hydrometallurgy recycling technologies within the UK. It estimated the break-even points for hydro and pyro processes to be in 2031 and 2033, respectively, highlighting the significant impact of transportation and logistics of spent batteries and providing information on the location of new plants. Further research [125] based on the energy and material flows evaluated the economic aspects of various spent battery recycling pathways, revealing that the capacity and material prices significantly influence the economic performance of recycling processes. This suggests a potential conflict of interest between large centralized facilities and rising transportation costs.
Overall, the economic analysis of spent battery recycling processes provides essential foundational data for technological innovation and the formation of business models in this field. This can serve as an important reference for future development directions of recycling technologies and policy-making, contributing to the establishment of sustainable spent battery management and recycling strategies.
Considering the outcomes of reviews on the impact of previous regulations and policies as well as economic aspect analyses, it is clear that there is an urgent need for innovation in the pyrometallurgical recycling technologies. In this context, the pyrometallurgical recycling process highlights the need for improvements to address the high energy consumption and greenhouse gas (GHG) emissions associated with traditional high-temperature smelting processes, as well as the loss of valuable metals like Li and Mn. One of the research directions being explored to address these issues involves novel technological innovations in the roasting process, which treats spent batteries at moderate temperatures below 1000°C. This process presents the potential to reduce energy consumption and GHG emissions while recovering most valuable metals.
Particularly, gas reduction reactions using green reductants such as hydrogen are attracting significant attention. This process, which is carbon-free and produces H2O as a byproduct, can drastically lower the temperature compared to traditional high-temperature smelting processes. Thanks to the high reduction potential of hydrogen, research is actively being conducted on its application in recycling LFP batteries, which have a stable olivine structure. This is becoming increasingly important as the need for recycling LFP batteries, which are more stable than NMC batteries, rises, although it is still in the early stages of research [130].
Studies [92,131–133] on the recovery of Li from LiCoO2 (LCO) and NCM cathode materials have evaluated the minimum reaction temperature to be above 500°C. This was verified by examining the amount recovered through water leaching, following the conversion of Li2O, separated from the cathode material by hydrogen, into water-soluble LiOH after reacting with H2O vapor, a reaction product. In this case, the recovery rate of Li was reported to increase with higher temperatures and hydrogen concentrations. However, recent studies based on actual spent-batteries undergoing hydrogen gas reduction have reported that higher temperatures lead to the production of more insoluble LiF salts due to the thermal decomposition of the PVDF binder material and the resulting HF gas, ultimately reducing the Li recovery rate [134]. On the other hand, for valuable metals such as Ni, Co, Mn, recovered through physical (magnetic separation) or hydrometallurgical (leaching) process in subsequent stages, the metallization rate is reported to have a significant impact on the recovery rate, with higher temperatures generally leading to increased recovery rates. Therefore, further research is necessary to optimize the recovery rates of Li and other valuable metals, particularly considering the cost and supply of hydrogen in the economic analysis.
Ammonia has been proposed as another green reductant, and recent studies have involved not only theoretical exploration but also verification through actual experiments [135]. The ammonia gas reduction mechanism for LCO cathode materials was elucidated through experiments using Thermo-Gravimetric (TG) analysis and thermodynamic calculations in the temperature range from 303 to 973 K.
Overall reaction of LCO reduction by NH3:
| \begin{aligned}[b]2\mathrm{L}\mathrm{i}\mathrm{C}\mathrm{o}{\mathrm{O}}_{2}\left(\mathrm{s}\right)& +2\mathrm{N}{\mathrm{H}}_{3}\left(\mathrm{g}\right)\to 2\mathrm{C}\mathrm{o}\left(\mathrm{s}\right)+3{\mathrm{H}}_{2}\mathrm{O}\left(\mathrm{g}\right)+\\ & {\mathrm{L}\mathrm{i}}_{2}\mathrm{O}\left(\mathrm{s}\right)+{\mathrm{N}}_{2}\left(\mathrm{g}\right) \end{aligned} | (17) |
Step-wise reduction:
| \begin{aligned}[b] 6\mathrm{L}\mathrm{i}\mathrm{C}\mathrm{o}{\mathrm{O}}_{2}\left(\mathrm{s}\right)&+2\mathrm{N}{\mathrm{H}}_{3}\left(\mathrm{g}\right)\to 6\mathrm{C}\mathrm{o}\mathrm{O}\left(\mathrm{s}\right)+3{\mathrm{H}}_{2}\mathrm{O}\left(\mathrm{g}\right)+\\ &{3\mathrm{L}\mathrm{i}}_{2}\mathrm{O}\left(\mathrm{s}\right)+{\mathrm{N}}_{2}\left(\mathrm{g}\right) \end{aligned} | (18) |
| 3\mathrm{C}\mathrm{o}\mathrm{O}\left(\mathrm{s}\right)+2\mathrm{N}{\mathrm{H}}_{3}\left(\mathrm{g}\right)\to 3\mathrm{C}\mathrm{o}\left(\mathrm{s}\right)+3{\mathrm{H}}_{2}\mathrm{O}\left(\mathrm{g}\right)+{\mathrm{N}}_{2}\left(\mathrm{g}\right) | (19) |
After the reduction process was completed, it was observed that lithium and cobalt had been transformed into distinct compounds: lithium as Li2CO3 and cobalt as its elemental metallic form. This discovery was significant since, by employing water leaching techniques, an impressive recovery rate of up to 99.96% for lithium was achieved.
A key breakthrough was realized from the vantage point of Oxygen elements removal (OER). Here, the O-cage digestion mechanism was postulated. This mechanism, visually represented in Fig. 12, provides a comprehensive framework to understand metal extraction from the spent lithium-ion batteries. This mechanism emphasizes that the type of reductant chosen can have profound impacts on the overall metal extraction efficiency. For instance, when weaker reductants were employed, the results demonstrated a relatively diminished selectivity for lithium. In stark contrast, stronger reductants showcased a heightened selectivity for lithium. These revelations are not just academic; they offer practical implications for enhancing lithium recovery. The anticipation in the research community is palpable, with hopes that these findings, once fully harnessed, could extend the ammonia reduction technique’s applicability to an array of cathode materials, not just confined to LCO.
Lastly, selective sulfidation has recently been gaining attention as another novel process [136]. Selective sulfidation has been proposed as a groundbreaking technique for effectively separating mixed-metal oxide compounds, and it has been confirmed, as shown in Fig. 13, that it results in the separation into three phases: Ni-rich sulfide, Co-rich sulfide, and Mn oxysulfide, following selective sulfidation. Subsequent proposals for physical separation methods such as froth flotation and magnetic separation seek economic and environmental benefits compared to conventional processes, and very encouraging results have been observed for the challenging separation of Ni and Co through sulfide electrolysis [137].
As the global emphasis on carbon neutrality and eco-friendly issues intensifies, the electric vehicle market is experiencing rapid expansion. This expansion naturally leads to an explosive increase in the demand for lithium-ion batteries. However, this growth also raises concerns about the monopoly and shortage of critical resources like lithium, as well as the generation and disposal of waste batteries. To address these issues, there is active commercialization and research into recycling technologies, especially those based on pyrometallurgy and hydrometallurgy.
Reviews of existing pyrometallurgical recycling technologies highlight their advantageous position due to their ability to process large volumes without the need for pre-treatment. However, the competitiveness of these technologies is challenged by the energy consumption and greenhouse gas (GHG) emissions associated with the high-temperature smelting process, as well as the loss of elements such as Li and Mn. These issues are also reflected in regulations and policies concerning lithium-ion batteries and recycling technologies, as well as economic analyses. Regulations and policies in various countries are strengthening the obligation to recycle lithium-ion batteries, leading to an increase in the volume of battery recycling. While this could positively impact pyrometallurgical recycling technologies, the requirement for minimum recovery rates for individual material components and the mandatory reduction of carbon footprints demand further innovation to enhance the competitiveness of these technologies.
Economic analyses also show that while economies of scale associated with large-volume processing can lead to profit increases, excessive energy consumption and Li losses act as obstacles to profit growth. This highlights the urgent need for solutions. In response to these issues, recent attention has been given to the development of eco-friendly, moderate-temperature roasting-based recycling technologies, as opposed to high-temperature processes. In particular, gas reduction methods using green reductants like hydrogen and ammonia can lower process temperatures without CO2 emissions, reduce Li losses, and enable the recovery of valuable metals. However, research on these technologies with actual batteries is still in its initial stages, and there is a need for advanced physical separation processes for the recovery of valuable metals and carbon following roasting. The application of new technologies like selective sulfidation is still in the preliminary research phase but shows potential for the development of economical and environmentally friendly recycling technologies.
In conclusion, pyrometallurgical recycling technologies have the potential to play a significant role in the field of battery recycling but require continuous research and innovation to overcome current drawbacks and challenges. To enhance the sustainability and economic viability of recycling technologies, regulatory improvements and the stimulation of technological innovation through collaboration between industry, academia, and government are crucial. Such efforts will significantly contribute to accelerating the transition to a sustainable future and realizing a resource-circulating economy.
This work was financially supported by the Technology Innovation Program (or Industrial Strategic Technology Development Program) and the Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea (No. 20022950).
Il Sohn is an editorial board member for this journal and was not involved in the editorial review or the decision to publish this article. All authors do not have competing interests to declare.
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| 1. | Junjie Shi, Changle Hou, Jingjing Dong, et al. Low-temperature chlorination roasting technology for the simultaneous recovery of valuable metals from spent LiCoO2 cathode material. International Journal of Minerals, Metallurgy and Materials, 2025, 32(1): 80. DOI:10.1007/s12613-024-2898-4 |
| 2. | Afzal Ahmed Dar, Zhi Chen, Gaixia Zhang, et al. Sustainable Extraction of Critical Minerals from Waste Batteries: A Green Solvent Approach in Resource Recovery. Batteries, 2025, 11(2): 51. DOI:10.3390/batteries11020051 |
| 3. | Peter Cornelius Gantz, Louisa Panjiyar, Andreas Neumann, et al. Lithium‐Phase Identification in an Industrial Lithium‐Ion‐Battery Recycling Slag: Implications for the Recovery of Lithium. Advanced Energy and Sustainability Research, 2024. DOI:10.1002/aesr.202400338 |
| 4. | Jin Zhang, Ding Chen, Jixiang Jiao, et al. Valorization of spent lithium-ion battery cathode materials for energy conversion reactions. Green Energy & Environment, 2024. DOI:10.1016/j.gee.2024.10.006 |
Figures(13) / Tables(1)
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| Company | Capacity / (t⋅a−1) | Products | Li recovery | Ref |
| Umicore | Ni, Co, Cu, Fe, CoCl2, Ni(OH)2 | Loss | [118–119] | |
| Glencore | Co–Ni–Cu alloy | Loss | [118,120] | |
| Inmetco | Co–Ni–Fe alloy | Loss | [51,121] | |
| Accurec | Co–Ni–Mn–Fe alloy Li3CO3 | 50% | [51,118] | |
| JX Nippon Mining and Metals | Ni, Co, Li2CO3, MnCO3 | 70% | [122] |
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