Special Issue "New Science Based Concepts for Increased Efficiency in Battery Recycling 2020"

A special issue of Metals (ISSN 2075-4701). This special issue belongs to the section "Extractive Metallurgy".

Deadline for manuscript submissions: closed (31 December 2020).

Special Issue Editor

Special Issue Information

Dear Colleagues,

There is no doubt that e-mobility will become a tremendous driving force for our future life. High demand for advanced materials in the batteries as well as political pressures in terms of collection and recycling rates raise the need for an extensive recovery of critical elements and a more sustainable use of raw materials. This Special Issue aims to make significant progress in designing innovative processes and understanding related mechanisms in the context of battery recycling. Although we expect the majority of papers to address the latest scientific achievements in the area of lithium-based systems, the entire range from lead, to nickel–metal–hydride, to high-temperature vanadium sodium cells is covered by this compilation. Of special interest are concepts for future post-Li-systems including all solid-state cell designs. We are not focusing on consumer behavior, collection, legal, and regulation issues and market development. Papers dealing with automized disassambly/dismantling, sensor-based sorting, new concepts for comminution and classification, thermal conditioning, innovations in hydro- and pyrometallurgical processing, safety aspects regarding recycling processes, post-mortem analysis with regards to cell chemistry changes, as well as mass flow analysis and optimization models for recycling efficiency are welcome.

The idea of a circular economy is the point of origin for contributions, aiming at minimizing of waste streams and promoting re-use/recirculation of components, functional materials as well as elements. In order to minimize material losses and energy consumption, this Issue explores concepts for optimization concerning the interfaces between mechanical and thermal pre-treatments with metallurgical processes. Considering both principle aspects of circular economy and material design, the topics of special interest are those concerning recovery and re-use of critical metals like lithium, since their importance for technological applications often goes along with a lack of supply on the world market.

Prof. Dr. Bernd Friedrich
Guest Editor

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Keywords

  • battery recycling
  • resource efficiency
  • circular economy
  • recovery
  • critical metals
  • waste minimization

Published Papers (20 papers)

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Editorial

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Editorial
New Science Based Concepts for Increased Efficiency in Battery Recycling
Metals 2021, 11(4), 533; https://doi.org/10.3390/met11040533 - 25 Mar 2021
Viewed by 614
Abstract
It is a common understanding worldwide that electromobility will have a significant share in passenger transport and that there will be a very dynamic increase in the return volumes of discarded batteries in the future [...] Full article
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Research

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Article
Task Planner for Robotic Disassembly of Electric Vehicle Battery Pack
Metals 2021, 11(3), 387; https://doi.org/10.3390/met11030387 - 26 Feb 2021
Cited by 2 | Viewed by 852
Abstract
The rapidly growing deployment of Electric Vehicles (EV) put strong demands on the development of Lithium-Ion Batteries (LIBs) but also into its dismantling process, a necessary step for circular economy. The aim of this study is therefore to develop an autonomous task planner [...] Read more.
The rapidly growing deployment of Electric Vehicles (EV) put strong demands on the development of Lithium-Ion Batteries (LIBs) but also into its dismantling process, a necessary step for circular economy. The aim of this study is therefore to develop an autonomous task planner for the dismantling of EV Lithium-Ion Battery pack to a module level through the design and implementation of a computer vision system. This research contributes to moving closer towards fully automated EV battery robotic dismantling, an inevitable step for a sustainable world transition to an electric economy. For the proposed task planner the main functions consist in identifying LIB components and their locations, in creating a feasible dismantling plan, and lastly in moving the robot to the detected dismantling positions. Results show that the proposed method has measurement errors lower than 5 mm. In addition, the system is able to perform all the steps in the order and with a total average time of 34 s. The computer vision, robotics and battery disassembly have been successfully unified, resulting in a designed and tested task planner well suited for product with large variations and uncertainties. Full article
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Article
The COOL-Process—A Selective Approach for Recycling Lithium Batteries
Metals 2021, 11(2), 259; https://doi.org/10.3390/met11020259 - 03 Feb 2021
Cited by 5 | Viewed by 3650
Abstract
The global market of lithium-ion batteries (LIB) has been growing in recent years, mainly owed to electromobility. The global LIB market is forecasted to amount to $129.3 billion in 2027. Considering the global reserves needed to produce these batteries and their limited lifetime, [...] Read more.
The global market of lithium-ion batteries (LIB) has been growing in recent years, mainly owed to electromobility. The global LIB market is forecasted to amount to $129.3 billion in 2027. Considering the global reserves needed to produce these batteries and their limited lifetime, efficient recycling processes for secondary sources are mandatory. A selective process for Li recycling from LIB black mass is described. Depending on the process parameters Li was recovered almost quantitatively by the COOL-Process making use of the selective leaching properties of supercritical CO2/water. Optimization of this direct carbonization process was carried out by a design of experiments (DOE) using a 33 Box-Behnken design. Optimal reaction conditions were 230 °C, 4 h, and a water:black mass ratio of 90 mL/g, yielding 98.6 ± 0.19 wt.% Li. Almost quantitative yield (99.05 ± 0.64 wt.%), yet at the expense of higher energy consumption, was obtained with 230 °C, 4 h, and a water:black mass ratio of 120 mL/g. Mainly Li and Al were mobilized, which allows for selectively precipitating Li2CO3 in battery grade-quality (>99.8 wt.%) without the need for further refining. Valuable metals, such as Co, Cu, Fe, Ni, and Mn, remained in the solid residue (97.7 wt.%), from where they are recovered by established processes. Housing materials were separated mechanically, thus recycling LIB without residues. This holistic zero waste-approach allows for recovering the critical raw material Li from both primary and secondary sources. Full article
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Article
Speciation of Manganese in a Synthetic Recycling Slag Relevant for Lithium Recycling from Lithium-Ion Batteries
Metals 2021, 11(2), 188; https://doi.org/10.3390/met11020188 - 21 Jan 2021
Cited by 3 | Viewed by 1014
Abstract
Lithium aluminum oxide has previously been identified to be a suitable compound to recover lithium (Li) from Li-ion battery recycling slags. Its formation is hampered in the presence of high concentrations of manganese (9 wt.% MnO2). In this study, mock-up slags [...] Read more.
Lithium aluminum oxide has previously been identified to be a suitable compound to recover lithium (Li) from Li-ion battery recycling slags. Its formation is hampered in the presence of high concentrations of manganese (9 wt.% MnO2). In this study, mock-up slags of the system Li2O-CaO-SiO2-Al2O3-MgO-MnOx with up to 17 mol% MnO2-content were prepared. The manganese (Mn)-bearing phases were characterized with inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray diffraction (XRD), electron probe microanalysis (EPMA), and X-ray absorption near edge structure analysis (XANES). The XRD results confirm the decrease of LiAlO2 phases from Mn-poor slags (7 mol% MnO2) to Mn-rich slags (17 mol% MnO2). The Mn-rich grains are predominantly present as idiomorphic and relatively large (>50 µm) crystals. XRD, EPMA and XANES suggest that manganese is present in the form of a spinel solid solution. The absence of light elements besides Li and O allowed to estimate the Li content in the Mn-rich grain, and to determine a generic stoichiometry of the spinel solid solution, i.e., (Li(2x)Mn2+(1−x))1+x(Al(2−z),Mn3+z)O4. The coefficients x and z were determined at several locations of the grain. It is shown that the aluminum concentration decreases, while the manganese concentration increases from the start (x: 0.27; z: 0.54) to the end (x: 0.34; z: 1.55) of the crystallization. Full article
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Article
Early-Stage Recovery of Lithium from Tailored Thermal Conditioned Black Mass Part I: Mobilizing Lithium via Supercritical CO2-Carbonation
Metals 2021, 11(2), 177; https://doi.org/10.3390/met11020177 - 20 Jan 2021
Cited by 2 | Viewed by 1238
Abstract
In the frame of global demand for electrical storage based on lithium-ion batteries (LIBs), their recycling with a focus on the circular economy is a critical topic. In terms of political incentives, the European legislative is currently under revision. Most industrial recycling processes [...] Read more.
In the frame of global demand for electrical storage based on lithium-ion batteries (LIBs), their recycling with a focus on the circular economy is a critical topic. In terms of political incentives, the European legislative is currently under revision. Most industrial recycling processes target valuable battery components, such as nickel and cobalt, but do not focus on lithium recovery. Especially in the context of reduced cobalt shares in the battery cathodes, it is important to investigate environmentally friendly and economic and robust recycling processes to ensure lithium mobilization. In this study, the method early-stage lithium recovery (“ESLR”) is studied in detail. Its concept comprises the shifting of lithium recovery to the beginning of the chemo-metallurgical part of the recycling process chain in comparison to the state-of-the-art. In detail, full NCM (Lithium Nickel Manganese Cobalt Oxide)-based electric vehicle cells are thermally treated to recover heat-treated black mass. Then, the heat-treated black mass is subjected to an H2O-leaching step to examine the share of water-soluble lithium phases. This is compared to a carbonation treatment with supercritical CO2, where a higher extent of lithium from the heat-treated black mass can be transferred to an aqueous solution than just by H2O-leaching. Key influencing factors on the lithium yield are the filter cake purification, the lithium separation method, the solid/liquid ratio, the pyrolysis temperature and atmosphere, and the setup of autoclave carbonation, which can be performed in an H2O-environment or in a dry autoclave environment. The carbonation treatments in this study are reached by an autoclave reactor working with CO2 in a supercritical state. This enables selective leaching of lithium in H2O followed by a subsequent thermally induced precipitation as lithium carbonate. In this approach, treatment with supercritical CO2 in an autoclave reactor leads to lithium yields of up to 79%. Full article
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Article
A Novel Pyrometallurgical Recycling Process for Lithium-Ion Batteries and Its Application to the Recycling of LCO and LFP
Metals 2021, 11(1), 149; https://doi.org/10.3390/met11010149 - 14 Jan 2021
Cited by 4 | Viewed by 1233
Abstract
The bottleneck of recycling chains for spent lithium-ion batteries (LIBs) is the recovery of valuable metals from the black matter that remains after dismantling and deactivation in pre‑treatment processes, which has to be treated in a subsequent step with pyrometallurgical and/or hydrometallurgical methods. [...] Read more.
The bottleneck of recycling chains for spent lithium-ion batteries (LIBs) is the recovery of valuable metals from the black matter that remains after dismantling and deactivation in pre‑treatment processes, which has to be treated in a subsequent step with pyrometallurgical and/or hydrometallurgical methods. In the course of this paper, investigations in a heating microscope were conducted to determine the high-temperature behavior of the cathode materials lithium cobalt oxide (LCO—chem., LiCoO2) and lithium iron phosphate (LFP—chem., LiFePO4) from LIB with carbon addition. For the purpose of continuous process development of a novel pyrometallurgical recycling process and adaptation of this to the requirements of the LIB material, two different reactor designs were examined. When treating LCO in an Al2O3 crucible, lithium could be removed at a rate of 76% via the gas stream, which is directly and purely available for further processing. In contrast, a removal rate of lithium of up to 97% was achieved in an MgO crucible. In addition, the basic capability of the concept for the treatment of LFP was investigated whereby a phosphorus removal rate of 64% with a simultaneous lithium removal rate of 68% was observed. Full article
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Article
Optimization of Manganese Recovery from a Solution Based on Lithium-Ion Batteries by Solvent Extraction with D2EHPA
Metals 2021, 11(1), 54; https://doi.org/10.3390/met11010054 - 29 Dec 2020
Cited by 5 | Viewed by 1215
Abstract
Manganese is a critical metal for the steelmaking industry, and it is expected that its world demand will be increasingly affected by the growing market of lithium-ion batteries. In addition to the increasing importance of manganese, its recycling is mainly determined by trends [...] Read more.
Manganese is a critical metal for the steelmaking industry, and it is expected that its world demand will be increasingly affected by the growing market of lithium-ion batteries. In addition to the increasing importance of manganese, its recycling is mainly determined by trends in the recycling of iron and steel. The recovery of manganese by solvent extraction has been widely investigated; however, the interaction of different variables affecting the process is generally not assessed. In this study, the solvent extraction of manganese from a solution based on lithium-ion batteries was modeled and optimized using factorial designs of experiments and the response surface methodology. Under optimized conditions (O:A of 1.25:1, pH 3.25, and 0.5 M bis(2-ethylhexyl) phosphoric acid (D2EHPA)), extractions above 70% Mn were reached in a single extraction stage with a coextraction of less than 5% Co, which was mostly removed in two scrubbing stages. A stripping product containing around 23 g/L Mn and around 0.3 g/L Co can be obtained under optimized conditions (O:A of 8:1, 1 M H2SO4 and around 13 min of contact time) in one stripping stage. Full article
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Article
Li-Distribution in Compounds of the Li2O-MgO-Al2O3-SiO2-CaO System—A First Survey
Metals 2020, 10(12), 1633; https://doi.org/10.3390/met10121633 - 04 Dec 2020
Cited by 4 | Viewed by 719
Abstract
The recovery of critical elements in recycling processes of complex high-tech products is often limited when applying only mechanical separation methods. A possible route is the pyrometallurgical processing that allows transferring of important critical elements into an alloy melt. Chemical rather ignoble elements [...] Read more.
The recovery of critical elements in recycling processes of complex high-tech products is often limited when applying only mechanical separation methods. A possible route is the pyrometallurgical processing that allows transferring of important critical elements into an alloy melt. Chemical rather ignoble elements will report in slag or dust. Valuable ignoble elements such as lithium should be recovered out of that material stream. A novel approach to accomplish this is enrichment in engineered artificial minerals (EnAM). An application with a high potential for resource efficient solutions is the pyrometallurgical processing of Li ion batteries. Starting from comparatively simple slag compositions such as the Li-Al-Si-Ca-O system, the next level of complexity is reached when adding Mg, derived from slag builders or other sources. Every additional component will change the distribution of Li between the compounds generated in the slag. Investigations with powder X-Ray diffraction (PXRD) and electron probe microanalysis (EPMA) of solidified melt of the five-compound system Li2O-MgO-Al2O3- SiO2-CaO reveal that Li can occur in various compounds from beginning to the end of the crystallization. Among these compounds are Li1−x(Al1−xSix)O2, Li1−xMgy(Al)(Al3/2y+xSi2−x−3/2y)O6, solid solutions of Mg1−(3/2y)Al2+yO4/LiAl5O8 and Ca-alumosilicate (melilite). There are indications of segregation processes of Al-rich and Si(Ca)-rich melts. The experimental results were compared with solidification curves via thermodynamic calculations of the systems MgO-Al2O3 and Li2O-SiO2-Al2O3. Full article
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Article
Investigation of Centrifugal Fractionation with Time-Dependent Process Parameters as a New Approach Contributing to the Direct Recycling of Lithium-Ion Battery Components
Metals 2020, 10(12), 1617; https://doi.org/10.3390/met10121617 - 01 Dec 2020
Cited by 4 | Viewed by 1158
Abstract
Recycling of lithium-ion batteries will become imperative in the future, but comprehensive and sustainable processes for this are still rather lacking. Direct recycling comprising separation of the black mass components as a key step is regarded as the most seminal approach. This paper [...] Read more.
Recycling of lithium-ion batteries will become imperative in the future, but comprehensive and sustainable processes for this are still rather lacking. Direct recycling comprising separation of the black mass components as a key step is regarded as the most seminal approach. This paper contributes a novel approach for such separation, that is fractionation in a tubular centrifuge. An aqueous dispersion of cathode materials (lithium iron phosphate, also referred to as LFP, and carbon black) serves as exemplary feed to be fractionated, desirably resulting in a sediment of pure LFP. This paper provides a detailed study of the commonly time-dependent output of the tubular centrifuge and introduces an approach aiming to achieve constant output. Therefore, three different settings are assessed, constantly low, constantly high and an increase in rotational speed over time. Constant settings result in the predictable unsatisfactory time-variant output, whereas rotational speed increase proves to be able to maintain constant centrate properties. With further process development, the concept of fractionation in tubular centrifuges may mature into a promising separation technique for black mass in a direct recycling process chain. Full article
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Article
A Combined Pyro- and Hydrometallurgical Approach to Recycle Pyrolyzed Lithium-Ion Battery Black Mass Part 2: Lithium Recovery from Li Enriched Slag—Thermodynamic Study, Kinetic Study, and Dry Digestion
Metals 2020, 10(11), 1558; https://doi.org/10.3390/met10111558 - 23 Nov 2020
Cited by 5 | Viewed by 1472
Abstract
Due to the increasing demand for battery raw materials, such as cobalt, nickel, manganese, and lithium, the extraction of these metals, not only from primary, but also from secondary sources, is becoming increasingly important. Spent lithium-ion batteries (LIBs) represent a potential source of [...] Read more.
Due to the increasing demand for battery raw materials, such as cobalt, nickel, manganese, and lithium, the extraction of these metals, not only from primary, but also from secondary sources, is becoming increasingly important. Spent lithium-ion batteries (LIBs) represent a potential source of raw materials. One possible approach for an optimized recovery of valuable metals from spent LIBs is a combined pyro- and hydrometallurgical process. The generation of mixed cobalt, nickel, and copper alloy and lithium slag as intermediate products in an electric arc furnace is investigated in part 1. Hydrometallurgical recovery of lithium from the Li slag is investigated in part 2 of this article. Kinetic study has shown that the leaching of slag in H2SO4 takes place according to the 3-dimensional diffusion model and the activation energy is 22–24 kJ/mol. Leaching of the silicon from slag is causing formation of gels, which complicates filtration and further recovery of lithium from solutions. The thermodynamic study presented in the work describes the reasons for the formation of gels and the possibilities of their prevention by SiO2 precipitation. Based on these findings, the Li slag was treated by the dry digestion (DD) method followed by dissolution in water. The silicon leaching efficiency was significantly reduced from 50% in the direct leaching experiment to 5% in the DD experiment followed by dissolution, while the high leaching efficiency of lithium was maintained. The study takes into account the preparation of solutions for the future trouble-free acquisition of marketable products from solutions. Full article
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Article
Recycling Strategies for Ceramic All-Solid-State Batteries—Part I: Study on Possible Treatments in Contrast to Li-Ion Battery Recycling
Metals 2020, 10(11), 1523; https://doi.org/10.3390/met10111523 - 17 Nov 2020
Cited by 4 | Viewed by 1211
Abstract
In the coming years, the demand for safe electrical energy storage devices with high energy density will increase drastically due to the electrification of the transportation sector and the need for stationary storage for renewable energies. Advanced battery concepts like all-solid-state batteries (ASBs) [...] Read more.
In the coming years, the demand for safe electrical energy storage devices with high energy density will increase drastically due to the electrification of the transportation sector and the need for stationary storage for renewable energies. Advanced battery concepts like all-solid-state batteries (ASBs) are considered one of the most promising candidates for future energy storage technologies. They offer several advantages over conventional Lithium-Ion Batteries (LIBs), especially with regard to stability, safety, and energy density. Hardly any recycling studies have been conducted, yet, but such examinations will play an important role when considering raw materials supply, sustainability of battery systems, CO2 footprint, and general strive towards a circular economy. Although different methods for recycling LIBs are already available, the transferability to ASBs is not straightforward due to differences in used materials and fabrication technologies, even if the chemistry does not change (e.g., Li-intercalation cathodes). Challenges in terms of the ceramic nature of the cell components and thus the necessity for specific recycling strategies are investigated here for the first time. As a major result, a recycling route based on inert shredding, a subsequent thermal treatment, and a sorting step is suggested, and transferring the extracted black mass to a dedicated hydrometallurgical recycling process is proposed. The hydrometallurgical approach is split into two scenarios differing in terms of solubility of the ASB-battery components. Hence, developing a full recycling concept is reached by this study, which will be experimentally examined in future research. Full article
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Article
Recycling Potential of Lithium–Sulfur Batteries—A First Concept Using Thermal and Hydrometallurgical Methods
Metals 2020, 10(11), 1513; https://doi.org/10.3390/met10111513 - 13 Nov 2020
Cited by 2 | Viewed by 971
Abstract
High-energy battery systems are gaining attention in the frame of global demands for electronic devices and vehicle electrification. This context leads to higher demands in terms of battery system properties, such as cycle stability and energy density. Here, Lithium–Sulfur (Li–S) batteries comprise an [...] Read more.
High-energy battery systems are gaining attention in the frame of global demands for electronic devices and vehicle electrification. This context leads to higher demands in terms of battery system properties, such as cycle stability and energy density. Here, Lithium–Sulfur (Li–S) batteries comprise an alternative to conventional Li-Ion battery (LIB) systems and can be asserted to next-generation electric storage systems. They offer a promising solution for contemporary needs, especially for applications requiring a higher energy density. In a global environment with increasing sustainable economics and ambitions towards commodity recirculation, the establishing of new technologies should also be evaluated in terms of their recycling potential. In this sense, innovative recycling considers highly valuable metals but also mobilizes all technologically relevant materials for reaching a high Recycling Efficiency (RE). This study uses an approach in which the recycling of Li–S batteries is addressed. For this purpose, a holistic recycling process using both thermal and hydrometallurgical steps is suggested for a safe treatment in combination with a maximum possible recycling efficiency. According to the batteries’ chemical composition, the containing elements are recovered separately, while a multi-step treatment is chosen. Hence, a thermal treatment in combination with a subsequent mechanical comminution separates a black mass powder containing all recoverable resources from the metal casing. The black mass is then treated further in an aqueous solution using different solid/liquid ratios: 1:20, 1:50, 1:55, and 1:100. Different basic and acidic leaching solutions are compared with one another: sulfuric acid (H2SO4), nitric acid (HNO3), hydrochloric acid (HCl), and NaOH. For further precipitation steps, different additives for a pH adjustment are also contrasted: sodium hydroxide (NaOH) and potassium hydroxide (KOH). The results are evaluated by both purity and yield; chemical analysis is performed by ICP-OES (inductively coupled plasma optical emission spectrometry). The aim of this recycling process comprises a maximum yield for the main Li–S battery fractions: Li, S, C, and Al. The focal point for the evaluation comprises lithium yields, and up to 93% of lithium could be transferred to a solid lithium carbonate product. Full article
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Article
Selective Precipitation of Metal Oxalates from Lithium Ion Battery Leach Solutions
Metals 2020, 10(11), 1435; https://doi.org/10.3390/met10111435 - 29 Oct 2020
Cited by 2 | Viewed by 894
Abstract
The separation of cobalt and nickel from sulfatic leach liquors of spent lithium-ion batteries is described in this paper. In addition to the base metals (e.g., cobalt and nickel), components such as manganese and lithium are also present in such leach liquors. The [...] Read more.
The separation of cobalt and nickel from sulfatic leach liquors of spent lithium-ion batteries is described in this paper. In addition to the base metals (e.g., cobalt and nickel), components such as manganese and lithium are also present in such leach liquors. The co-precipitation of these contaminants can be prevented during leach liquor processing by selective precipitation. For the recovery of a cobalt-nickel mixed material, oxalic acid serves as a suitable reagent. For the optimization of the precipitation retention time and yield, the dependence of the oxalic acid addition must be taken into account. In addition to efficiency, attention must also be given to the purity of the product. After this procedure, further processing of the products by calcination into oxides leads to better marketability. A series of experiments confirms the suitability of oxalic acid for precipitation of cobalt and nickel as a mixed oxalate from sulfatic liquors and also suggests a possible route for further processing of the products with increased marketability. The impurities in the resulting oxides are below 3%, whereby a sufficiently high purity of the mixed oxide can be achieved. Full article
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Article
A Combined Pyro- and Hydrometallurgical Approach to Recycle Pyrolyzed Lithium-Ion Battery Black Mass Part 1: Production of Lithium Concentrates in an Electric Arc Furnace
Metals 2020, 10(8), 1069; https://doi.org/10.3390/met10081069 - 07 Aug 2020
Cited by 6 | Viewed by 4509
Abstract
Due to the increasing demand for battery raw materials such as cobalt, nickel, manganese, and lithium, the extraction of these metals not only from primary, but also from secondary sources like spent lithium-ion batteries (LIBs) is becoming increasingly important. One possible approach for [...] Read more.
Due to the increasing demand for battery raw materials such as cobalt, nickel, manganese, and lithium, the extraction of these metals not only from primary, but also from secondary sources like spent lithium-ion batteries (LIBs) is becoming increasingly important. One possible approach for an optimized recovery of valuable metals from spent LIBs is a combined pyro- and hydrometallurgical process. According to the pyrometallurgical process route, in this paper, a suitable slag design for the generation of slag enriched by lithium and mixed cobalt, nickel, and copper alloy as intermediate products in a laboratory electric arc furnace was investigated. Smelting experiments were carried out using pyrolyzed pelletized black mass, copper(II) oxide, and different quartz additions as a flux to investigate the influence on lithium-slagging. With the proposed smelting operation, lithium could be enriched with a maximum yield of 82.4% in the slag, whereas the yield for cobalt, nickel, and copper in the metal alloy was 81.6%, 93.3%, and 90.7% respectively. The slag obtained from the melting process is investigated by chemical and mineralogical characterization techniques. Hydrometallurgical treatment to recover lithium is carried out with the slag and presented in part 2. Full article
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Article
Disassembly of Li Ion Cells—Characterization and Safety Considerations of a Recycling Scheme
Metals 2020, 10(6), 773; https://doi.org/10.3390/met10060773 - 09 Jun 2020
Cited by 13 | Viewed by 3950
Abstract
It is predicted there will be a rapid increase in the number of lithium ion batteries reaching end of life. However, recently only 5% of lithium ion batteries (LIBs) were recycled in the European Union. This paper explores why and how this can [...] Read more.
It is predicted there will be a rapid increase in the number of lithium ion batteries reaching end of life. However, recently only 5% of lithium ion batteries (LIBs) were recycled in the European Union. This paper explores why and how this can be improved by controlled dismantling, characterization and recycling. Currently, the favored disposal route for batteries is shredding of complete systems and then separation of individual fractions. This can be effective for the partial recovery of some materials, producing impure, mixed or contaminated waste streams. For an effective circular economy it would be beneficial to produce greater purity waste streams and be able to re-use (as well as recycle) some components; thus, a dismantling system could have advantages over shredding. This paper presents an alternative complete system disassembly process route for lithium ion batteries and examines the various processes required to enable material or component recovery. A schematic is presented of the entire process for all material components along with a materials recovery assay. Health and safety considerations and options for each stage of the process are also reported. This is with an aim of encouraging future battery dismantling operations. Full article
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Article
Integrating Flotation and Pyrometallurgy for Recovering Graphite and Valuable Metals from Battery Scrap
Metals 2020, 10(5), 680; https://doi.org/10.3390/met10050680 - 21 May 2020
Cited by 10 | Viewed by 2036
Abstract
Since the current volumes of collected end-of-life lithium ion batteries (LIBs) are low, one option to increase the feasibility of their recycling is to feed them to existing metals production processes. This work presents a novel approach to integrate froth flotation as a [...] Read more.
Since the current volumes of collected end-of-life lithium ion batteries (LIBs) are low, one option to increase the feasibility of their recycling is to feed them to existing metals production processes. This work presents a novel approach to integrate froth flotation as a mechanical treatment to optimize the recovery of valuable metals from LIB scrap and minimize their loss in the nickel slag cleaning process. Additionally, the conventional reducing agent in slag cleaning, namely coke, is replaced with graphite contained in the LIB waste flotation products. Using proper conditioning procedures, froth flotation was able to recover up to 81.3% Co in active materials from a Cu-Al rich feed stream. A selected froth product was used as feed for nickel slag cleaning process, and the recovery of metals from a slag (80%)–froth fraction (20%) mixture was investigated in an inert atmosphere at 1350 °C and 1400 °C at varying reduction times. The experimental conditions in combination with the graphite allowed for a very rapid reduction. After 5 min reduction time, the valuable metals Co, Ni, and Cu were found to be distributed to the iron rich metal alloy, while the remaining fraction of Mn and Al present in the froth fraction was deported in the slag. Full article
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Article
Cleaner Recycling of Spent Lead-Acid Battery Paste and Co-Treatment of Pyrite Cinder via a Reductive Sulfur-Fixing Method for Valuable Metal Recovery and Sulfur Conservation
Metals 2019, 9(8), 911; https://doi.org/10.3390/met9080911 - 20 Aug 2019
Cited by 5 | Viewed by 1392
Abstract
This study proposes a cleaner lead-acid battery (LAB) paste and pyrite cinder (PyC) recycling method without excessive generation of SO2. PyCs were employed as sulfur-fixing reagents to conserve sulfur as condensed sulfides, which prevented SO2 emissions. In this work, the [...] Read more.
This study proposes a cleaner lead-acid battery (LAB) paste and pyrite cinder (PyC) recycling method without excessive generation of SO2. PyCs were employed as sulfur-fixing reagents to conserve sulfur as condensed sulfides, which prevented SO2 emissions. In this work, the phase transformation mechanisms in a PbSO4-Na2CO3-Fe3O4-C reaction system were studied in detail. Furthermore, the co-treatment of spent LAB and PyCs was conducted to determine the optimal recycling conditions and to detect the influences of different processing parameters on lead recovery and sulfur fixation. In addition, a bench-scale experiment was carried out to confirm the feasibility and reliability of this novel process. The results reveal that the products were separated into three distinct layers: slag, ferrous matte, and crude lead. 98.3% of lead and 99% of silver in the feed materials were directly enriched in crude lead. Crude lead with purity of more than 98 wt.% (weight percent) was obtained by a one-step extraction. Lead contents in the produced matte and slag were below 2.7 wt.% and 0.6 wt.%, respectively. At the same time, 99.2% total sulfur was fixed and recovered. Full article
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Review

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Review
Challenges in Ecofriendly Battery Recycling and Closed Material Cycles: A Perspective on Future Lithium Battery Generations
Metals 2021, 11(2), 291; https://doi.org/10.3390/met11020291 - 08 Feb 2021
Cited by 6 | Viewed by 2364
Abstract
The global use of lithium-ion batteries of all types has been increasing at a rapid pace for many years. In order to achieve the goal of an economical and sustainable battery industry, the recycling and recirculation of materials is a central element on [...] Read more.
The global use of lithium-ion batteries of all types has been increasing at a rapid pace for many years. In order to achieve the goal of an economical and sustainable battery industry, the recycling and recirculation of materials is a central element on this path. As the achievement of high 95% recovery rates demanded by the European Union for some metals from today’s lithium ion batteries is already very challenging, the question arises of how the process chains and safety of battery recycling as well as the achievement of closed material cycles are affected by the new lithium battery generations, which are supposed to enter the market in the next 5 to 10 years. Based on a survey of the potential development of battery technology in the next years, where a diversification between high-performance and cost-efficient batteries is expected, and today’s knowledge on recycling, the challenges and chances of the new battery generations regarding the development of recycling processes, hazards in battery dismantling and recycling, as well as establishing a circular economy are discussed. It becomes clear that the diversification and new developments demand a proper separation of battery types before recycling, for example by a transnational network of dismantling and sorting locations, and flexible and high sophisticated recycling processes with case-wise higher safety standards than today. Moreover, for the low-cost batteries, recycling of the batteries becomes economically unattractive, so legal stipulations become important. However, in general, it must be still secured that closing the material cycle for all battery types with suitable processes is achieved to secure the supply of raw materials and also to further advance new developments. Full article
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Review
Industrial Recycling of Lithium-Ion Batteries—A Critical Review of Metallurgical Process Routes
Metals 2020, 10(8), 1107; https://doi.org/10.3390/met10081107 - 18 Aug 2020
Cited by 21 | Viewed by 5055
Abstract
Research for the recycling of lithium-ion batteries (LIBs) started about 15 years ago. In recent years, several processes have been realized in small-scale industrial plants in Europe, which can be classified into two major process routes. The first one combines pyrometallurgy with subsequent [...] Read more.
Research for the recycling of lithium-ion batteries (LIBs) started about 15 years ago. In recent years, several processes have been realized in small-scale industrial plants in Europe, which can be classified into two major process routes. The first one combines pyrometallurgy with subsequent hydrometallurgy, while the second one combines mechanical processing, often after thermal pre-treatment, with metallurgical processing. Both process routes have a series of advantages and disadvantages with respect to legislative and health, safety and environmental requirements, possible recovery rates of the components, process robustness, and economic factors. This review critically discusses the current status of development, focusing on the metallurgical processing of LIB modules and cells. Although the main metallurgical process routes are defined, some issues remain unsolved. Most process routes achieve high yields for the valuable metals cobalt, copper, and nickel. In comparison, lithium is only recovered in few processes and with a lower yield, albeit a high economic value. The recovery of the low value components graphite, manganese, and electrolyte solvents is technically feasible but economically challenging. The handling of organic and halogenic components causes technical difficulties and high costs in all process routes. Therefore, further improvements need to be achieved to close the LIB loop before high amounts of LIB scrap return. Full article
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Review
Recycling Chain for Spent Lithium-Ion Batteries
Metals 2020, 10(3), 316; https://doi.org/10.3390/met10030316 - 28 Feb 2020
Cited by 18 | Viewed by 3131
Abstract
The recycling of spent lithium-ion batteries (LIB) is becoming increasingly important with regard to environmental, economic, geostrategic, and health aspects due to the increasing amount of LIB produced, introduced into the market, and being spent in the following years. The recycling itself becomes [...] Read more.
The recycling of spent lithium-ion batteries (LIB) is becoming increasingly important with regard to environmental, economic, geostrategic, and health aspects due to the increasing amount of LIB produced, introduced into the market, and being spent in the following years. The recycling itself becomes a challenge to face on one hand the special aspects of LIB-technology and on the other hand to reply to the idea of circular economy. In this paper, we analyze the different recycling concepts for spent LIBs and categorize them according to state-of-the-art schemes of waste treatment technology. Therefore, we structure the different processes into process stages and unit processes. Several recycling technologies are treating spent lithium-ion batteries worldwide focusing on one or several process stages or unit processes. Full article
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