New Science Based Concepts for Increased Efficiency in Battery Recycling 2023

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

Deadline for manuscript submissions: closed (29 February 2024) | Viewed by 65370

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.

This Special Issue follows the 2020 issue, which can be found under
https://www.mdpi.com/journal/metals/special_issues/battery_recycling

Prof. Dr. Bernd Friedrich
Guest Editor

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Keywords

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

Published Papers (24 papers)

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14 pages, 4958 KiB  
Article
Modelling the Sorting of Lithium-Ion Battery Components in a Zig-Zag Air Classifier
by Alexandra Kaas, Christian Wilke, Johannes-Samuel Rabaschus, Thomas Mütze and Urs A. Peuker
Metals 2024, 14(3), 269; https://doi.org/10.3390/met14030269 - 24 Feb 2024
Viewed by 1002
Abstract
The recycling of lithium-ion batteries, in particular, has become increasingly important in recent years. Due to the materials contained, such as copper or nickel, the return to the economic cycle is important. To ensure this, binding measures have been introduced by the European [...] Read more.
The recycling of lithium-ion batteries, in particular, has become increasingly important in recent years. Due to the materials contained, such as copper or nickel, the return to the economic cycle is important. To ensure this, binding measures have been introduced by the European Commission. As part of the mechanical recycling of lithium-ion batteries, the zig-zag air classifier is used to separate battery components. One application is the separation of the current conductor foils from each other, which is investigated and modelled here. Existing models deriving from the literature are evaluated for material fractions coming from the recycling of different automotive lithium-ion batteries. Since the separation depends on the geometry of the foil particles, similarities for separation depending on the geometric characteristics of the electrodes are derived. It turns out that the material is too complex for the empirical model. However, the model can be used to evaluate the suitability of the apparatus and the quality of the separation. Full article
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12 pages, 2579 KiB  
Article
Spectral Characterization of Battery Components from Li-Ion Battery Recycling Processes
by Julia Richter, Sandra Lorenz, Alexandra Kaas, Margret Fuchs, Christian Röder, Urs A. Peuker, Johannes Heitmann and Richard Gloaguen
Metals 2024, 14(2), 147; https://doi.org/10.3390/met14020147 - 25 Jan 2024
Viewed by 1274
Abstract
Considering the increasing demand for Li-ion batteries, there is a need for sophisticated recycling strategies with both high recovery rates and low costs. Applying optical sensors for automating component detection is a very promising approach because of the non-contact, real-time process monitoring and [...] Read more.
Considering the increasing demand for Li-ion batteries, there is a need for sophisticated recycling strategies with both high recovery rates and low costs. Applying optical sensors for automating component detection is a very promising approach because of the non-contact, real-time process monitoring and the potential for complete digitization of mechanical sorting processes. In this work, mm-scale particles from shredded end-of-life Li-ion batteries are investigated by five different reflectance sensors, and a range from the visible to long-wave infrared is covered to determine the ideal detection window for major component identification as relevant input signals to sorting technologies. Based on the characterization, a spectral library including Al, Cu, separator foil, inlay foil, and plastic splinters was created, and the visible to near-infrared range (400–1000 nm) was identified as the most suitable spectral range to reliably discriminate between Al, Cu, and other battery components in the recycling material stream of interest. The evaluation of the different sensor types outlines that only imaging sensors meet the requirements of recycling stream monitoring and can deliver sufficient signal quality for subsequent mechanical sorting controls. Requirements for the setup parameters were discussed leading to the setup recommendation of a fast snapshot camera with a sufficiently high spectral resolution and signal-to-noise ratio. Full article
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13 pages, 3681 KiB  
Article
An Electrochemical Approach to the Recovery of Metals Typical of Battery Waste
by Claudia Kutzer-Schulze, Hannes Schmidt, Mathias Weiser, Tilo Büttner, Michael Schneider and Alexander Michaelis
Metals 2024, 14(1), 109; https://doi.org/10.3390/met14010109 - 16 Jan 2024
Viewed by 989
Abstract
This paper deals with the separate electrochemical recovery of transition metals from battery black liquor. In a first approach, the authors investigated a model waste electrolyte mainly consisting of Cu, Co, Ni, and Mn in an acidic solvent, using citric acid as a [...] Read more.
This paper deals with the separate electrochemical recovery of transition metals from battery black liquor. In a first approach, the authors investigated a model waste electrolyte mainly consisting of Cu, Co, Ni, and Mn in an acidic solvent, using citric acid as a complexing agent. An open porous Inconel® foam had been included as an electrode to benefit from the increased active surface area. Under the selected operation conditions, Cu was completely recovered, presenting almost 100% purity, while, in the case of Co, the purity was 96%, and a remanent concentration of about 1.2 g L−1 could still be determined. Full article
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13 pages, 1765 KiB  
Article
Co-Precipitation of Metal Oxalates from Organic Leach Solution Derived from Spent Lithium-Ion Batteries (LIBs)
by Dominik Schmitz, Hariaman Prasetyo, Alexander Birich, Rungsima Yeetsorn and Bernd Friedrich
Metals 2024, 14(1), 80; https://doi.org/10.3390/met14010080 - 9 Jan 2024
Cited by 1 | Viewed by 1720
Abstract
Recent studies in hydrometallurgy are focused on developing eco-friendly and selective leach agents such as organic acids. These agents can extract metal ions, which are usually separated through precipitation methods. When traditional methods are used, the separation is complex and time-consuming, and each [...] Read more.
Recent studies in hydrometallurgy are focused on developing eco-friendly and selective leach agents such as organic acids. These agents can extract metal ions, which are usually separated through precipitation methods. When traditional methods are used, the separation is complex and time-consuming, and each metal cation is required to be isolated separately. Moreover, extracted metal salts are subsequently recombined in the regeneration of cathode materials. To simplify this, a novel simultaneous precipitation approach has been developed, allowing the separation of metal salts that can directly contribute to regenerating novel cathode materials, bypassing the need for separate isolation. This study aimed to recover cobalt, nickel, and manganese from the organic leach solution of spent lithium-ion batteries (LIBs) through co-precipitation of metal oxalates. The investigation includes the selection of organic acids and the best parameters for the leaching process, as well as testing different molar ratios of the metals M2+ (M = Co, Ni, Mn) to oxalic acid (1:3, 1:4.5, 1:6, and 1:7.5) to examine the effects of the precipitating agent on the recovery percentages of the metals. The findings indicate that 2 M citric acid and 4 vol% H2O2 is the optimal parameter in the leaching process. Meanwhile, in the co-precipitation process, an increase in the molar ratio leads to a corresponding rise in the resulting metal recoveries. At the ratio of 1:7.5, cobalt, nickel, and manganese were recovered to the extent of 99.26%, 98.93%, and 94.01%, respectively. Nevertheless, at the increased molar ratio, the co-extraction of lithium and aluminum was observed, resulting in reduced selectivity and decreased precipitate purity. Full article
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14 pages, 2015 KiB  
Article
Transfer of Early-Stage Lithium Recovery from Laboratory-Scale Water Leaching to Upscale Challenges
by Daniel Dotto Munchen, Ksenija Milicevic Neumann, Ilayda Elif Öner and Bernd Friedrich
Metals 2024, 14(1), 67; https://doi.org/10.3390/met14010067 - 6 Jan 2024
Viewed by 1390
Abstract
The early-stage lithium recovery (ESLR) process associates thermal treatment of the black mass from lithium-ion batteries (LIB) with subsequent leaching, especially with water, targeting Li recovery in the first step of the process chain as lithium carbonate. The validation of ESLR has resulted [...] Read more.
The early-stage lithium recovery (ESLR) process associates thermal treatment of the black mass from lithium-ion batteries (LIB) with subsequent leaching, especially with water, targeting Li recovery in the first step of the process chain as lithium carbonate. The validation of ESLR has resulted in high Li efficiencies; however, currently, researchers have not yet been established the optimum parameters, which brings uncertainties to a further upscale. Based on that, four parameters, including different black masses previously thermally treated in the industry, were investigated in a leaching step in laboratory scale targeting Li and F leaching efficiencies. Through ANOVA statistical analysis, regression equations of the leaching efficiencies for both elements were generated, which supports an optimization study. The optimum parameters were then transferred to an upscale 100 L leaching trial and evaluated. The results in laboratory scale showed that Li maximization and F minimization were achieved at an S/L ratio of 30 g/L, 80 °C, and 6 L/min of CO2 gas addition, as well as with a sample of bigger particle size and probably more efficient thermal treatment. However, the upscale result with the same parameters showed a lower Li leaching efficiency, which is related to the poor geometric similarity between laboratory and upscale reactors. Full article
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21 pages, 13325 KiB  
Article
Holistic Investigation of the Inert Thermal Treatment of Industrially Shredded NMC 622 Lithium-Ion Batteries and Its Influence on Selective Lithium Recovery by Water Leaching
by Christin Stallmeister and Bernd Friedrich
Metals 2023, 13(12), 2000; https://doi.org/10.3390/met13122000 - 12 Dec 2023
Cited by 2 | Viewed by 1298
Abstract
The thermal treatment of lithium-ion batteries is an already industrially implemented process step in some recycling chains. It provides the advantages of controlled organic removal and conditioning of the black mass for further process steps, such as water-based early-stage lithium recovery. Therefore, a [...] Read more.
The thermal treatment of lithium-ion batteries is an already industrially implemented process step in some recycling chains. It provides the advantages of controlled organic removal and conditioning of the black mass for further process steps, such as water-based early-stage lithium recovery. Therefore, a deep understanding of ongoing reactions and the influence of the process parameters on the reaction products is crucial. This study investigates the inert thermal treatment of an industrial end-of-life NMC 622 battery shredder in a 200 g scale regarding the influence of process parameters on the reaction products, separation of black mass, and its water leaching. Therefore, the off-gas produced during the thermal treatment was analyzed by FTIR, and afterwards, a sieve classification of the shredder was carried out. The separated black mass was further analyzed for residual organics by pyrolysis GC-MS and for its phase composition by XRD. A water leaching of the different thermally treated black masses was carried out for Li recovery. Occurring reactions during the thermal treatment process, such as the different stages of organic removal and reduction reactions in the active material, were derived based on the collected data. These reactions mainly affect the water-based Li recovery, which is related to Li2CO3 generation. The maximum pyrolysis temperature has the greatest effect on the Li recovery. After a treatment at 642 °C, 62.4% of Li was leached. Reactions of the co-elements F, P and Al with Li during the thermal treatment were identified as the limiting factors regarding Li recovery. Full article
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18 pages, 6192 KiB  
Article
Influence of the Cell Type on the Physical Processes of the Mechanical Recycling of Automotive Lithium-Ion Batteries
by Christian Wilke, Alexandra Kaas and Urs Alexander Peuker
Metals 2023, 13(11), 1901; https://doi.org/10.3390/met13111901 - 17 Nov 2023
Cited by 2 | Viewed by 1217
Abstract
Lithium-Ion Battery (LIB) manufacturers produce different cell formats (prismatic, cylindrical, pouch, etc.) with different casing materials (steel or aluminium) and cell chemistries (e.g., NMC, NCA, LFP, etc.) for application in electric vehicles. By law, these cells have to be recycled after their lifetime. [...] Read more.
Lithium-Ion Battery (LIB) manufacturers produce different cell formats (prismatic, cylindrical, pouch, etc.) with different casing materials (steel or aluminium) and cell chemistries (e.g., NMC, NCA, LFP, etc.) for application in electric vehicles. By law, these cells have to be recycled after their lifetime. This study investigates the influence of different cell types on the outcome of a standardized mechanical recycling process consisting of crushing, sieving and air classification. The aim of the study is to find out whether different cell types can be processed together or whether the recovery and product quality can be improved by processing them separately. Pouch cells require low energy consumption for crushing compared to cylindrical and prismatic cells. Steel as a casing material increases the energy requirement during crushing compared to aluminium. The particle size distribution of several product fractions varies significantly between the different cell types. During air classification, the separator, anode, and cathode show a similar separation behaviour and can be processed with the same settings, whereas for the separation of the casing metals, different settling velocities need to be applied depending on the casing material. Full article
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21 pages, 9131 KiB  
Article
Gluconic Acid Leaching of Spent Lithium-Ion Batteries as an Environmentally Friendly Approach to Achieve High Leaching Efficiencies in the Recycling of NMC Active Material
by Reinhard Lerchbammer, Eva Gerold and Helmut Antrekowitsch
Metals 2023, 13(8), 1330; https://doi.org/10.3390/met13081330 - 25 Jul 2023
Cited by 5 | Viewed by 1562
Abstract
Organic acids, such as gluconic acid, have been widely studied for their potential in the hydrometallurgical recycling of lithium-ion batteries. These organic alternative leachants offer several environmental and recycling-related benefits, including a high selectivity in terms of dissolving valuable metals, as well as [...] Read more.
Organic acids, such as gluconic acid, have been widely studied for their potential in the hydrometallurgical recycling of lithium-ion batteries. These organic alternative leachants offer several environmental and recycling-related benefits, including a high selectivity in terms of dissolving valuable metals, as well as a reduced environmental impact due to the application of non-toxic and biodegradable organic acids. Gluconic acid has previously been demonstrated in the oxidative degradation of glucose, either as an alternative reducing agent or in biometallurgical approaches, and has been described as an efficiency-supporting reagent. The results of this study demonstrate the effectiveness of using gluconic acid for the recovery of metals such as lithium, cobalt, nickel, and manganese from spent lithium-ion batteries. Recovery rates of above 98% for lithium, cobalt, and manganese, and a recovery rate of more than 80% for nickel could be reached by optimizing the leaching parameters, including an acid concentration of 1.2 M, the addition of hydrogen peroxide of 1.6 vol %, a solid-to-liquid ratio of 25 g/L, a leaching temperature of 75 °C, and a leaching time of 192 min. These results show that gluconic acid has the potential to become a viable and sustainable option for the hydrometallurgical recycling of lithium-ion batteries, as well as for opening a possible biohydrometallurgical route. Further investigations are required into the results obtained, to verify the existence of a new hydrometallurgical and sustainable process route involving gluconic acid. Full article
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14 pages, 3909 KiB  
Article
Acid-Assisted Separation of Cathodic Material from Spent Electric Vehicle Batteries for Recycling
by Anton Zorin, Tengfei Song, Dominika Gastol and Emma Kendrick
Metals 2023, 13(7), 1276; https://doi.org/10.3390/met13071276 - 15 Jul 2023
Cited by 2 | Viewed by 1726
Abstract
The recycling of lithium-ion batteries presents challenges due to the complex composition of waste streams generated by current processes. Achieving higher purity levels, particularly in the reclamation of aluminium metal and transition metal black mass, is essential for improved valorisation. In this study, [...] Read more.
The recycling of lithium-ion batteries presents challenges due to the complex composition of waste streams generated by current processes. Achieving higher purity levels, particularly in the reclamation of aluminium metal and transition metal black mass, is essential for improved valorisation. In this study, we propose a high-efficiency, low-energy, and environmentally friendly method using organic acids to separate cathodic black mass from the aluminium current collector. The acids selected in this study all show >86% peeling efficiency with acetic acid showing 100% peeling efficiency of black mass from the current collector. The recovered materials were subjected to X-ray diffraction, electron microscopy, and elemental analysis techniques. We show that oxalic-acid-treated material exhibited two distinct active material components with a minimal change in mass ratio compared to the untreated material. We show by elemental analysis of the leachates that the majority of critical materials were retained in the black mass and limited aluminium was leached during the process, with almost 100% of Al recovery achieved. This methodology enables the production of high-purity concentrated aluminium and critical metal feedstocks (Mn, Co, Ni, and Li) for further hydro-metallurgical processes, upcycling of the cathode material, and direct recycling. The proposed approach offers significant potential for enhancing valorization in lithium-ion battery recycling, facilitating efficient separation and optimal recovery of valuable metals. Full article
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14 pages, 4307 KiB  
Article
A Detailed Kinetic Analysis of the Environmentally Friendly Leaching of Spent Lithium-Ion Batteries Using Monocarboxylic Acid
by Sibananda Sahu, Subhankar Pati and Niharbala Devi
Metals 2023, 13(5), 947; https://doi.org/10.3390/met13050947 - 13 May 2023
Cited by 2 | Viewed by 1539
Abstract
It is essential to develop a leaching procedure that uses minimal acid consumption, is economical, recovers large amounts of metal, and has a minimal negative impact on the environment. In this paper, a viable hydrometallurgical method using acetic acid as a leachant is [...] Read more.
It is essential to develop a leaching procedure that uses minimal acid consumption, is economical, recovers large amounts of metal, and has a minimal negative impact on the environment. In this paper, a viable hydrometallurgical method using acetic acid as a leachant is suggested for recovering critical metals from waste LCO-type batteries. Several leaching parameters were examined in order to optimize the leaching conditions. With 1.2 mol/L acetic acid, 7% H2O2, 90 °C, an S/L ratio of 10 g/L, and a 60 min leaching period, the maximum leaching efficiencies of Li (99.6%) and Co (95.6%) were attained. By investigating the different kinetic models, it was feasible to figure out the reaction’s pace, as well as the mechanism involved in the leaching process. It was found, through the comprehensive kinetic studies of the leaching process, that the surface chemical reaction controls the leaching mechanism for waste LCO-type batteries. The economic viability of the current leaching procedure in comparison to those of earlier approaches is also discussed. Full article
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17 pages, 2800 KiB  
Article
Acid Leaching of Al- and Ta-Substituted Li7La3Zr2O12 (LLZO) Solid Electrolyte
by Kirstin Schneider, Vivien Kiyek, Martin Finsterbusch, Bengi Yagmurlu and Daniel Goldmann
Metals 2023, 13(5), 834; https://doi.org/10.3390/met13050834 - 24 Apr 2023
Cited by 4 | Viewed by 2224
Abstract
Solid-state batteries (SSBs) are promising next-generation batteries due to their potential for achieving high energy densities and improved safety compared to conventional lithium-ion batteries (LIBs) with a flammable liquid electrolyte. Despite their huge market potential, very few studies have investigated SSB recycling processes [...] Read more.
Solid-state batteries (SSBs) are promising next-generation batteries due to their potential for achieving high energy densities and improved safety compared to conventional lithium-ion batteries (LIBs) with a flammable liquid electrolyte. Despite their huge market potential, very few studies have investigated SSB recycling processes to recover and reuse critical raw metals for a circular economy. For conventional LIBs, hydrometallurgical recycling has been proven to be able to produce high-quality products, with leaching being the first unit operation. Therefore, it is essential to establish a fundamental understanding of the leaching behavior of solid electrolytes as the key component of SSBs with different lixiviants. This work investigates the leaching of the most promising Al- and Ta-substituted Li7La3Zr2O12 (LLZO) solid electrolytes in mineral acids (H2SO4 and HCl), organic acids (formic, acetic, oxalic, and citric acid), and water. The leaching experiments were conducted using actual LLZO production waste in 1 M of acid at 1:20 S/L ratio at 25 °C for 24 h. The results showed that strong acids, such as H2SO4, almost completely dissolved LLZO. Encouraging selective leaching properties were observed with oxalic acid and water. This fundamental knowledge of LLZO leaching behavior will provide the basis for future optimization studies to develop innovative hydrometallurgical SSB recycling processes. Full article
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15 pages, 5588 KiB  
Article
Evaluation of the Influence Exerted by Increased Silicon Contents on the Leaching Behavior of NMC-Based Black Mass
by Eva Gerold, Reinhard Lerchbammer and Helmut Antrekowitsch
Metals 2023, 13(4), 785; https://doi.org/10.3390/met13040785 - 17 Apr 2023
Cited by 1 | Viewed by 1162
Abstract
The further development of lithium-ion batteries leads to an improvement in power densities as well as safety and thus requires an optimization of the materials used. For this purpose, among other approaches, the anode materials are doped with silicon oxide or metallic silicon [...] Read more.
The further development of lithium-ion batteries leads to an improvement in power densities as well as safety and thus requires an optimization of the materials used. For this purpose, among other approaches, the anode materials are doped with silicon oxide or metallic silicon is used as the anode. However, silicon is a semimetal and is known to lead to the formation of jelly-like fluids in hydrometallurgical processes under certain conditions. This publication evaluates which parameters are responsible for this viscosity change in the leaching solutions during the recycling of lithium-ion batteries and examines the corresponding reaction mechanism behind this phenomenon. Furthermore, the leaching efficiency for the valuable metals nickel, cobalt, lithium and manganese is evaluated and the influence of different silicon contents in the solution is investigated. It could be shown that, especially the simultaneous presence of H2SO4, H2O2 and Si or SiO2, lead to a significant viscosity increase due to the formation of metasilicic acid and, accordingly, the leaching efficiencies of the valuable metals are negatively influenced. Full article
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19 pages, 5197 KiB  
Article
Selective Sulfation Roasting for Cobalt and Lithium Extraction from Industrial LCO-Rich Spent Black Mass
by Jayasree Biswas, Sofia Ulmala, Xingbang Wan, Jere Partinen, Mari Lundström and Ari Jokilaakso
Metals 2023, 13(2), 358; https://doi.org/10.3390/met13020358 - 10 Feb 2023
Cited by 5 | Viewed by 2622
Abstract
The extraction of cobalt from secondary resources has become crucial, as cobalt has been identified as a strategically important and critical raw material due to the high risks of supply chain disruptions. In this work, selective sulfation roasting was investigated as a potential [...] Read more.
The extraction of cobalt from secondary resources has become crucial, as cobalt has been identified as a strategically important and critical raw material due to the high risks of supply chain disruptions. In this work, selective sulfation roasting was investigated as a potential recycling strategy to extract cobalt and lithium from an industrial lithium cobalt oxide (LCO)-rich black mass. Additionally, the effect of graphite on metal extraction was studied. In the first set of experiments, the sieved black mass fraction containing both cathode and anode materials was directly roasted in a predetermined composition of gas mixtures of SO2, O2, and Ar for 1 h at 850 °C. The gas composition was determined from Kellogg’s diagram to allow for the selective sulfation of Co and Li. In another set of experiments, the carbon present in the black mass was first removed by roasting the material in Ar for 2 h and then in an Ar and O2 gas mixture for five hours at 600 °C. Afterward, selective sulfation roasting was performed in mixtures of SO2, O2, and Ar gas similar to the previous set of experiments. For comparison, similar experiments were performed at 800 °C. The sulfation roasted black mass was leached in water to study the efficiency of Co extraction into the solution. Interestingly, the presence of carbon was found to be beneficial for Co extraction. The extraction efficiency for the first case (with carbon present in the raw material) was observed to be more than three times higher than in the second case (with carbon removed) for sulfation at 850 °C. The extraction efficiency and purity of the extracted Co were found to be better for higher temperature sulfation roasting conditions due to faster reaction kinetics. It was also found that almost all of the Li could be recovered while extracting Co. The maximum efficiency of the extraction was 99.51% Li and 61.21% Co for roasting under a gas flow of 10% SO2-10% O2-Ar at 850 °C for 60 min. These results suggest that Co and Li can be selectively extracted from the black mass by sulfation roasting pre-treatment followed by leaching in water. In holistic processing, the leach residue can then be further subjected to battery metal processing by state-of-the-art methods. Full article
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10 pages, 3366 KiB  
Article
Thermodynamics of Vacuum Chloride Volatilization of Ni, Co, Mn, Li, Al, and Cu in Spent Lithium−Ion Battery
by Wen Luo, Guochen Hu, Junshuai Ding, Jijun Wu and Wenhui Ma
Metals 2022, 12(12), 2183; https://doi.org/10.3390/met12122183 - 19 Dec 2022
Viewed by 1362
Abstract
In recent years the chlorination leaching separation process in the field of hydrometallurgy has been developed considerably. However, the development of the chlorination separation process in the field of pyrometallurgy has lagged. In this paper, the thermodynamics of vacuum chlorination volatilization of valuable [...] Read more.
In recent years the chlorination leaching separation process in the field of hydrometallurgy has been developed considerably. However, the development of the chlorination separation process in the field of pyrometallurgy has lagged. In this paper, the thermodynamics of vacuum chlorination volatilization of valuable metals Ni, Co, Mn, Li, Al, and Cu from spent lithium−ion batteries is investigated, and it is found that chlorination helps to achieve the trapping and separation of the singlet metals. With the help of Factsage 8.1, a theoretical map of the stable regions of valuable metal chlorides, the order of separation of each chloride at 10 Pa, and a discussion of the behavior of excess CuCl2 in the system at different temperatures were determined. This paper provides research ideas in the fields of selective separation of alloying elements in the carbothermal reduction products of waste lithium−ion batteries and one−step separation of valuable metals by carbothermal reduction. Full article
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24 pages, 5452 KiB  
Article
Optimization of a Pyrometallurgical Process to Efficiently Recover Valuable Metals from Commercially Used Lithium-Ion Battery Cathode Materials LCO, NCA, NMC622, and LFP
by Alexandra Holzer, Lukas Wiszniewski, Stefan Windisch-Kern and Harald Raupenstrauch
Metals 2022, 12(10), 1642; https://doi.org/10.3390/met12101642 - 29 Sep 2022
Cited by 4 | Viewed by 3125
Abstract
With an ever-growing demand for critical raw materials for the production of lithium-ion batteries and a price increase of respective commodities, an ever louder call from the industry for efficient recycling technologies can be noticed. So far, state-of-the-art industry-scaled pyrometallurgical recycling technologies all [...] Read more.
With an ever-growing demand for critical raw materials for the production of lithium-ion batteries and a price increase of respective commodities, an ever louder call from the industry for efficient recycling technologies can be noticed. So far, state-of-the-art industry-scaled pyrometallurgical recycling technologies all suffer from the same bottleneck of lithium slagging. At the Chair of Thermal Processing Technology at Montanuniversitaet Leoben, a novel reactor was developed to recover lithium and phosphorus via the gas phase in a pyrometallurgical process. Critical elements such as Li, Ni, Co, and Mn of the commercially used cathode materials LCO (LiCoO2), LFP (LiFePO4), NCA (LiNi0.8Co0.15Al0.05O2), and NMC622 (LiNi0.6Mn0.2Co0.2) were analyzed in a batch version of the so-called InduRed reactor concept. The analyses underline that the reactor concept is highly suitable for an efficient recovery for the metals Ni and Co and that slagging of Li can not only be largely prohibited, but the elements lithium and phosphorous can even be recovered from the gas phase. Plant engineering issues were also considered for further development toward a continuous process. The MgO crucible used shows significant diffusion of various elements from the battery material, which is why the choice of crucible material still requires in-depth research. Full article
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21 pages, 6112 KiB  
Article
Environmentally Friendly Recovery of Lithium from Lithium–Sulfur Batteries
by Lilian Schwich and Bernd Friedrich
Metals 2022, 12(7), 1108; https://doi.org/10.3390/met12071108 - 28 Jun 2022
Cited by 7 | Viewed by 3303
Abstract
In the context of the rising demand for electric storage systems, lithium–sulfur batteries provide an attractive solution for low-weight and high-energy battery systems. Considering circular economy for new technologies, it is necessary to assure the raw material requirements for future generations. Therefore, metallurgical [...] Read more.
In the context of the rising demand for electric storage systems, lithium–sulfur batteries provide an attractive solution for low-weight and high-energy battery systems. Considering circular economy for new technologies, it is necessary to assure the raw material requirements for future generations. Therefore, metallurgical recycling processes are required. Since lithium is the central and most valuable element used in lithium–sulfur batteries, this study presents an environmentally friendly and safe process for lithium recovery as lithium carbonate. The developed and experimentally performed process is a combination of thermal and hydrometallurgical methods. Firstly, the battery cells are thermally deactivated to mechanically extract black mass. Then, water leaching of the black mass in combination with using CO2, instead of emitting it, can mobilize lithium by >90% as solid product. Full article
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18 pages, 4625 KiB  
Article
Fractionation of Transition Metals by Solvent Extraction and Precipitation from Tannic Acid-Acetic Acid Leachate as a Product of Lithium-Ion Battery Leaching
by Erik Prasetyo, Corby Anderson, Arya Fitra Jaya, Widya Aryani Muryanta, Anton Sapto Handoko, Muhammad Amin, Muhammad Al Muttaqii and Fathan Bahfie
Metals 2022, 12(5), 882; https://doi.org/10.3390/met12050882 - 23 May 2022
Cited by 1 | Viewed by 1994
Abstract
Solvent extraction and precipitation schemes are applied to isolate copper, cobalt, manganese and nickel from leachate, produced from spent lithium-ion battery leaching using tannic acid-acetic acid as lixiviant. The metal separation and purification were developed based on a ketoxime (LIX® 84-I) and [...] Read more.
Solvent extraction and precipitation schemes are applied to isolate copper, cobalt, manganese and nickel from leachate, produced from spent lithium-ion battery leaching using tannic acid-acetic acid as lixiviant. The metal separation and purification were developed based on a ketoxime (LIX® 84-I) and a phosphinic acid (Cyanex® 272) extraction system. Aside from the leachate’s initial pH, which dictates the metal isolation flowsheet, other parameters affecting metal extraction rate, such as phase ratio, extractant concentration, and acid stripping will be evaluated. Copper was selectively removed from leachate at pH 3, using LIX® 84-I 10% v/v followed by cobalt and manganese co-extraction from the raffinate using Cyanex® 272 10% v/v at pH 5. After both metals were stripped using sulfuric acid 0.2 M, manganese was quantitatively precipitated out from the strip solution using potassium permanganate or sodium hypochlorite. Nickel was isolated using LIX® 84-I from raffinate at pH 5, producing a lithium- rich solution for further treatment. No third phase was formed during the extraction, and sulfuric acid was proved suitable for organic phase regeneration. Full article
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17 pages, 5257 KiB  
Article
Recovery of Graphite and Cathode Active Materials from Spent Lithium-Ion Batteries by Applying Two Pretreatment Methods and Flotation Combined with a Rapid Analysis Technique
by Hao Qiu, Christoph Peschel, Martin Winter, Sascha Nowak, Johanna Köthe and Daniel Goldmann
Metals 2022, 12(4), 677; https://doi.org/10.3390/met12040677 - 15 Apr 2022
Cited by 12 | Viewed by 3891
Abstract
This work investigates the comprehensive recycling of graphite and cathode active materials (LiNi0.6Mn0.2Co0.2O2, abbreviated as NMC) from spent lithium-ion batteries via pretreatment and flotation. Specific analytical methods (SPME-GC-MS and Py-GC-MS) were utilized to identify and [...] Read more.
This work investigates the comprehensive recycling of graphite and cathode active materials (LiNi0.6Mn0.2Co0.2O2, abbreviated as NMC) from spent lithium-ion batteries via pretreatment and flotation. Specific analytical methods (SPME-GC-MS and Py-GC-MS) were utilized to identify and trace the relevant influencing factors. Two different pretreatment methods, which are Fenton oxidation and roasting, were investigated with respect to their influence on the flotation effectiveness. As a result, for NMC cathode active materials, a recovery of 90% and a maximum grade of 83% were obtained by the optimized roasting and flotation. Meanwhile, a graphite grade of 77% in the froth product was achieved, with a graphite recovery of 75%. By using SPME-GC-MS and Py-GC-MS analyses, it could be shown that, in an optimized process, an effective destruction/removal of the electrolyte and binder residues can be reached. The applied analytical tools could be integrated into the workflow, which enabled process control in terms of the pretreatment sufficiency and achievable separation in the subsequent flotation. Full article
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29 pages, 8440 KiB  
Article
Recovering Value from End-of-Life Batteries by Integrating Froth Flotation and Pyrometallurgical Copper-Slag Cleaning
by Tommi Rinne, Anna Klemettinen, Lassi Klemettinen, Ronja Ruismäki, Hugh O’Brien, Ari Jokilaakso and Rodrigo Serna-Guerrero
Metals 2022, 12(1), 15; https://doi.org/10.3390/met12010015 - 22 Dec 2021
Cited by 8 | Viewed by 3354
Abstract
In this study, industrial lithium-ion battery (LIB) waste was treated by a froth flotation process, which allowed selective separation of electrode particles from metallic-rich fractions containing Cu and Al. In the flotation experiments, recovery rates of ~80 and 98.8% for the cathode active [...] Read more.
In this study, industrial lithium-ion battery (LIB) waste was treated by a froth flotation process, which allowed selective separation of electrode particles from metallic-rich fractions containing Cu and Al. In the flotation experiments, recovery rates of ~80 and 98.8% for the cathode active elements (Co, Ni, Mn) and graphite were achieved, respectively. The recovered metals from the flotation fraction were subsequently used in high-temperature Cu-slag reduction. In this manner, the possibility of using metallothermic reduction for Cu-slag reduction using Al-wires from LIB waste as the main reductant was studied. The behavior of valuable (Cu, Ni, Co, Li) and hazardous metals (Zn, As, Sb, Pb), as a function of time as well as the influence of Cu-slag-to-spent battery (SB) ratio, were investigated. The results showcase a suitable process to recover copper from spent batteries and industrial Cu-slag. Cu-concentration decreased to approximately 0.3 wt.% after 60 min reduction time in all samples where Cu/Al-rich LIB waste fraction was added. It was also showed that aluminothermic reduction is effective for removing hazardous metals from the slag. The proposed process is also capable of recovering Cu, Co, and Ni from both Cu-slag and LIB waste, resulting in a secondary Cu slag that can be used in various applications. Full article
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16 pages, 2457 KiB  
Article
Comparative Study for Selective Lithium Recovery via Chemical Transformations during Incineration and Dynamic Pyrolysis of EV Li-Ion Batteries
by Srija Balachandran, Kerstin Forsberg, Tom Lemaître, Nathália Vieceli, Gabriele Lombardo and Martina Petranikova
Metals 2021, 11(8), 1240; https://doi.org/10.3390/met11081240 - 4 Aug 2021
Cited by 10 | Viewed by 3152
Abstract
Selective leaching of Li from spent LIBs thermally pretreated by pyrolysis and incineration between 400 and 700 °C for 30, 60, and 90 min followed by water leaching at high temperature and high L/S ratio was examined. During the thermal pretreatment Li2 [...] Read more.
Selective leaching of Li from spent LIBs thermally pretreated by pyrolysis and incineration between 400 and 700 °C for 30, 60, and 90 min followed by water leaching at high temperature and high L/S ratio was examined. During the thermal pretreatment Li2CO3 and LiF were leached. Along with Li salts, AlF3 was also found to be leached with an efficiency not higher than 3.5%. The time of thermal pretreatment did not have a significant effect on Li leaching efficiency. The leaching efficiency of Li was higher with a higher L/S ratio. At a higher leaching temperature (80 °C), the leaching of Li was higher due to an increase in the solubility of present Li salts. The highest Li leaching efficiency of nearly 60% was observed from the sample pyrolyzed at 700 °C for 60 min under the leaching condition L/S ratio of 20:1 mL g−1 at 80 °C for 3 h. Furthermore, the use of an excess of 10% of carbon in a form of graphite during the thermal treatment did not improve the leaching efficiency of Li. Full article
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13 pages, 2113 KiB  
Article
Recovering Lithium from the Cathode Active Material in Lithium-Ion Batteries via Thermal Decomposition
by Shunsuke Kuzuhara, Mina Ota, Fuka Tsugita and Ryo Kasuya
Metals 2020, 10(4), 433; https://doi.org/10.3390/met10040433 - 26 Mar 2020
Cited by 16 | Viewed by 4262
Abstract
In this study, calcination tests were performed on a mixed sample of lithium cobalt oxide and activated carbon at 300–1000 °C under an argon atmosphere. The tests were conducted to discover an effective method for recovering lithium and cobalt from the cathode active [...] Read more.
In this study, calcination tests were performed on a mixed sample of lithium cobalt oxide and activated carbon at 300–1000 °C under an argon atmosphere. The tests were conducted to discover an effective method for recovering lithium and cobalt from the cathode active material used in lithium-ion batteries. Additionally, the effect of soluble fluorine on the purification of lithium carbonate was investigated by the addition of lithium fluoride to an aqueous lithium hydroxide solution and a CO2 flow test was performed. The lithium recovery was ≥90% when the calcination occurred at temperatures of 500–600 °C. However, the percent recovery decreased at temperatures ≥700 °C. It was demonstrated that in order to increase the recovery while maintaining 99% purity of lithium carbonate in the recovered material, it was imperative to increase the temperature of the solution and to limit the F/Li ratio (mass%/mass%) in the solution to a value that did not exceed 0.05. Full article
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Review

Jump to: Research

23 pages, 5019 KiB  
Review
Recycling Strategies for Spent Consumer Lithium-Ion Batteries
by Moritz Petzold and Sabine Flamme
Metals 2024, 14(2), 151; https://doi.org/10.3390/met14020151 - 25 Jan 2024
Cited by 1 | Viewed by 2343
Abstract
Introduction: In the quest for sustainable energy solutions and environmental protection, the management of end-of-life (EoL) batteries has emerged as a critical issue. Batteries, especially lithium-ion batteries (LIBs), power a wide range of devices and are central to modern life. As society’s reliance [...] Read more.
Introduction: In the quest for sustainable energy solutions and environmental protection, the management of end-of-life (EoL) batteries has emerged as a critical issue. Batteries, especially lithium-ion batteries (LIBs), power a wide range of devices and are central to modern life. As society’s reliance on batteries grows, there is an urgent need for sustainable battery recycling methods that can efficiently recover valuable materials, minimize environmental impact, and support the circular economy. Methods: A literature review was conducted to analyze the LIB market, the estimated return volumes and state-of-the-art sorting and recycling processes. Furthermore, a manual dismantling and input analysis was done for consumer LIB. Results: The current recycling processes operate for individual cathode active material input only. However, there is no sorting process or application in place to provide pre-sorted LIBs. This is why they need to be developed. X-ray transmission, X-ray fluorescence and optical sorting in theory can be applied to differentiate LIBs by their cathode active material. To support this hypothesis, further investigations need to be performed. Full article
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23 pages, 1618 KiB  
Review
Lithium Production and Recovery Methods: Overview of Lithium Losses
by Vladimír Marcinov, Jakub Klimko, Zita Takáčová, Jana Pirošková, Andrea Miškufová, Marcus Sommerfeld, Christian Dertmann, Bernd Friedrich and Dušan Oráč
Metals 2023, 13(7), 1213; https://doi.org/10.3390/met13071213 - 29 Jun 2023
Cited by 7 | Viewed by 6893
Abstract
The objective of this study is to describe primary lithium production and to summarize the methods for combined mechanical and hydrometallurgical recycling of lithium-ion batteries (LIBs). This study also aims to draw attention to the problem of lithium losses, which occur in individual [...] Read more.
The objective of this study is to describe primary lithium production and to summarize the methods for combined mechanical and hydrometallurgical recycling of lithium-ion batteries (LIBs). This study also aims to draw attention to the problem of lithium losses, which occur in individual recycling steps. The first step of hydrometallurgical treatment is leaching, which is an effective method capable of transferring over 99% of the present metals to the leach solutions. Extraction of metals after leaching can be conducted using various methods, with precipitation being the most commonly used. The precipitation of other metals can result in the co-precipitation of lithium, causing total lithium losses up to 30%. To prevent such losses, solvent extraction methods are used to selectively remove elements, such as Co, Ni, Al, and Mn. Solvent extraction (SX) is highly effective, reducing the losses to 3% per extraction stage and reducing overall lithium losses to 15%. After the refining, lithium is precipitated as lithium carbonate. High lithium carbonate solubility (1.5 g/L) and high liquid to solid leaching ratios require costly and avoidable operations to be implemented in order to enhance lithium concentration. Therefore, it is suggested that more studies should focus on multistage leaching with lower L/S ratios. Full article
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25 pages, 1470 KiB  
Review
Cobalt Recovery from Li-Ion Battery Recycling: A Critical Review
by Amilton Barbosa Botelho Junior, Srecko Stopic, Bernd Friedrich, Jorge Alberto Soares Tenório and Denise Crocce Romano Espinosa
Metals 2021, 11(12), 1999; https://doi.org/10.3390/met11121999 - 10 Dec 2021
Cited by 42 | Viewed by 9015
Abstract
The increasing demand for Li-ion batteries for electric vehicles sheds light upon the Co supply chain. The metal is crucial to the cathode of these batteries, and the leading global producer is the D.R. Congo (70%). For this reason, it is considered critical/strategic [...] Read more.
The increasing demand for Li-ion batteries for electric vehicles sheds light upon the Co supply chain. The metal is crucial to the cathode of these batteries, and the leading global producer is the D.R. Congo (70%). For this reason, it is considered critical/strategic due to the risk of interruption of supply in the short and medium term. Due to the increasing consumption for the transportation market, the batteries might be considered a secondary source of Co. The outstanding amount of spent batteries makes them to a core of urban mining warranting special attention. Greener technologies for Co recovery are necessary to achieve sustainable development. As a result of these sourcing challenges, this study is devoted to reviewing the techniques for Co recovery, such as acid leaching (inorganic and organic), separation (solvent extraction, ion exchange resins, and precipitation), and emerging technologies—ionic liquids, deep eutectic solvent, supercritical fluids, nanotechnology, and biohydrometallurgy. A dearth of research in emerging technologies for Co recovery from Li-ion batteries is discussed throughout the manuscript within a broader overview. The study is strictly connected to the Sustainability Development Goals (SDG) number 7, 8, 9, and 12. Full article
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