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Advances in the Geometallurgy of Battery Minerals
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Advances in the Geometallurgy of Battery Minerals

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Processing and Extractive Metallurgy".

Deadline for manuscript submissions: closed (15 November 2023) | Viewed by 26688

Special Issue Editors

Dr. Quentin Dehaine

E-Mail Website
Guest Editor
Circular Economy Solutions Unit, Circular Raw Materials Hub, Geological Survey of Finland, F1-02151 Espoo, Finland
Interests: geometallurgy; battery minerals; cobalt; rare earths elements; mineral processing; process mineralogy; theory of sampling; traceability; circular economy
Prof. Dr. Alan R. Butcher

E-Mail Website
Guest Editor
Circular Economy Solutions Unit, Circular Raw Materials Hub, Geological Survey of Finland, F1-02151 Espoo, Finland
Interests: geoanalytical techniques; battery minerals
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

We are at the cutting-edge of the electric revolution. Society needs to shift from a fossil fuel-based economy to a mineral-based one. Through the use of rechargeable batteries, consumer electronics, energy storage systems and electric mobility, and the availability of battery raw materials as well as the social and environmental impacts of mining, these materials have focussed attention on the need for dramatic production increases in order to meet the projected global demand. In the context of apparently declining ore grades and increasing ore complexity (fined-grained, mineralogically-intricated and poly-metallic ores), paired with rising environmental, social and governance (ESG) issues, the extractive minerals industry is facing one of its most challenging times ever seen. Therefore, ensuring resource efficiency all along the entire raw materials value chain, through the application of integrated holistic approaches, has been of growing interest for the mining, metallurgy and recycling industries in recent years, and is key to the success of the Circular Economy paradigm. It is only through the application of integrated approaches such as geometallurgy, but also life-cycle assessment (LCA) and traceability, encompassing the entire value chain, that our society will reach a low carbon economy with technologies which are truly sustainable from cradle to grave.

This Special Issue aims at compiling research in geometallurgy, but also all the above-mentioned research areas, applied to key battery raw materials, notably, but not restricted to, nickel, lithium, cobalt, graphite and magnesium. We welcome geological, mineralogical, mineral processing, environmental and recycling studies, both experimental, as well as theoretical, which integrate cross-disciplinarily aspects. We also solicit methodological studies employing cutting-edge technologies and analytical methods. We hope that this Special Issue will contribute to the achievement of a better understanding of the geometallurgy of battery minerals, their extraction and processing, as well as their sustainable and responsible sourcing.

Dr. Quentin Dehaine & Prof. Alan R. Butcher
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • battery minerals
  • geometallurgy
  • lithium
  • nickel
  • cobalt
  • sustainability

Published Papers (6 papers)

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Research

24 pages, 7893 KiB  
Article
Characterization and Liberation Study of the Beauvoir Granite for Lithium Mica Recovery
by Bastien Demeusy, Carlos Andrés Arias-Quintero, Gaëlle Butin, Juliette Lainé, Sunil Kumar Tripathy, Jérôme Marin, Quentin Dehaine and Lev O. Filippov
Minerals 2023, 13(7), 950; https://doi.org/10.3390/min13070950 - 17 Jul 2023
Cited by 2 | Viewed by 2478
Abstract
A significant proportion of Europe’s lithium endowment is hosted by unconventional lithium resources such as rare-metal granites (RMG) of which the Beauvoir granite in France is a prime example. In such hard-rock deposits, where lithium is mostly hosted in micas (lepidolite, zinnwaldite), the [...] Read more.
A significant proportion of Europe’s lithium endowment is hosted by unconventional lithium resources such as rare-metal granites (RMG) of which the Beauvoir granite in France is a prime example. In such hard-rock deposits, where lithium is mostly hosted in micas (lepidolite, zinnwaldite), the ability to assess whether lithium can be extracted economically from the ore is essential and requires a comprehensive understanding of mineralogical properties and lithium deportment. Using three exploratory drill cores distributed along the North–South axis, a preliminary geometallurgical assessment of the granite has been conducted based on a combination of techniques including Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), Atomic Adsorption Spectroscopy (AAS), Electron Probe Microanalysis (EPMA), Scanning Electron Microscope (SEM) coupled with automated mineralogy software, X-Ray Diffraction (XRD), optical microscope and sieving. Lithium distribution appears to be variable, reflecting the evolution of the granite, with higher mica content in the southern area and higher Li grade towards the center of the orebody. The size of micas in the assessed sample does not vary significantly. The grindability and liberation size of micas varies in the different zones investigated, PERC S being the most difficult to grind. There is always more than 50 wt% of the micas that are liberated in the samples when crushed to 1 mm. Indirect estimation of Li content based on EPMA and SEM analysis suggests that the content of lithium inside mica crystals could vary. If this estimation is confirmed by direct Li measurement, it for sure makes the calculations of the Li deportment more challenging. Full article
(This article belongs to the Special Issue Advances in the Geometallurgy of Battery Minerals)
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22 pages, 4593 KiB  
Article
Geometallurgy of Cobalt Black Ores in the Katanga Copperbelt (Ruashi Cu-Co Deposit): A New Proposal for Enhancing Cobalt Recovery
by Pascal Mambwe, Michel Shengo, Théophile Kidyanyama, Philippe Muchez and Mumba Chabu
Minerals 2022, 12(3), 295; https://doi.org/10.3390/min12030295 - 26 Feb 2022
Cited by 8 | Viewed by 4520
Abstract
Copper-cobalt deposits in the Central African Copperbelt belong to the Sediment-Hosted Stratiform Copper (SHSC) type and are situated in the Neoproterozoic Katanga Supergroup. This paper describes in detail the geology, geochemistry and hydrometallurgy of cobalt, with a special focus on the Black Ore [...] Read more.
Copper-cobalt deposits in the Central African Copperbelt belong to the Sediment-Hosted Stratiform Copper (SHSC) type and are situated in the Neoproterozoic Katanga Supergroup. This paper describes in detail the geology, geochemistry and hydrometallurgy of cobalt, with a special focus on the Black Ore Mineralised Zone (BOMZ) unit from the Ruashi Cu-Co deposit as a case study. Based on results from fieldwork and laboratory testing, it was concluded that the BOMZ consists of a succession of massive and stratified dolostones, which are weathered into carbonaceous clay dolostones and clays. The Lower “Calcaire à Minéreaux Noirs Formation” (Lower CMN Formation) consists of stratified and finely laminated dolostones, which are weathered at the surface into clayey to siliceous dolostones. The cobalt concentration in the weathering zone is due to supergene enrichment, a process that is linked to the formation of a cobalt cap. The ore consists of heterogenite associated with minor amounts of chrysocolla and malachite. Minor carrollite, chalcopyrite, chalcocite and bornite are present in unweathered fragments. The cobalt grade in both the BOMZ and Lower CMN decreases within depth while the copper grade increases. These grade changes reflect the variation in mineralogy with depth from heterogenite with minor amounts of malachite and chrysocolla to malachite, chrysocolla with traces of heterogenite, spherocobaltite, chalcocite, chalcopyrite, carrollite and bornite. Based on the Cu (100xAS Cu/TCu) and Co ratio (100 xAS Co/TCo), which is related to the ore mineralogy, oxide ores (Cu ratio ≥ 75%) and oxide dominant mixed ores (Cu ratio < 75%, containing the copper sulphide chalcocite) can be differentiated in both the BOMZ and Lower CMN. The absence of talc and the low concentration of Ni, Mn and Fe, on the one hand, and the high-grade Cu in the BOMZ, on the other hand, facilitate the hydrometallurgy of cobalt but require a specific processing. Consequently, the recovery of Co from the BOMZ requires the application of a processing method that is based on sulphuric acid (30 g/L) leaching under reducing conditions (300–350 mV) and the removal of impurities (Cu > 95% and Mn ≈ 99%) from the pregnant leach solution (PLS) by solvent extraction (SX) prior to the precipitation of cobalt as a high-grade hydroxide (40.5%). The sulphuric acid leaching of the BOMZ enabled achieving, after 8 h of magnetic stirring (500 rpm), a highest yield of 93% Co, with other major elements Mn (84%) and Cu (40%). The latter forms a main co-product of the Co exploitation. In contrast, the highest leaching yield for Fe remained smaller than 5%. Full article
(This article belongs to the Special Issue Advances in the Geometallurgy of Battery Minerals)
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14 pages, 2961 KiB  
Article
Multi-Technique Analytical Approach to Quantitative Analysis of Spodumene
by Lorenza Sardisco, Pyry-Mikko Hannula, Tim J. Pearce and Luke Morgan
Minerals 2022, 12(2), 175; https://doi.org/10.3390/min12020175 - 29 Jan 2022
Cited by 2 | Viewed by 3130
Abstract
The aim of this study was to establish the capability of X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) methods to determine different spodumene forms (α-, β- and γ-spodumene) occurring during heat treatment of lithium spodumene. It is essential to correctly identify [...] Read more.
The aim of this study was to establish the capability of X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) methods to determine different spodumene forms (α-, β- and γ-spodumene) occurring during heat treatment of lithium spodumene. It is essential to correctly identify and quantify the presence of different forms of spodumene after heat treatment to ensure optimum lithium extraction. A sample from the Haapaluoma lithium-pegmatite (western Finland) was used for this study. An experimental programme was initiated to model the progression of the mineral transformation at different stages through heat treatment. The specimen was broken down and split into five portions. One of the splits was analysed unheated with XRD, FTIR, XRF and ICP; the other four splits were analysed with XRD and FTIR after heat treatment at different temperatures from 850 to 1100 °C. In this study, we show that both laboratory-based XRD and portable FTIR methods are effective in identifying and quantifying α-, β- and γ-spodumene as well as impurities. The accuracy of the quantification of the minerals with XRD was established by using a mass balance calculation and was compared with the actual chemistry of the sample measured with ICP analysis. Fully quantitative XRD analysis of heat-treated spodumene is considered a challenge due to peak overlaps between the β-, and γ-spodumene forms, particularly when gangue minerals and amorphous content are present. The novelty of this study consists of the use of the XRD technique complemented by the Rietveld method to fully quantify the different forms of spodumene from one another: α-, β- and γ-spodumene, along with the gangue minerals and the amorphous content. It is also shown that reproducible systematic changes occur in the FTIR spectra that track the spodumene transformation during heat treatment. With more samples and cross-validation between the XRD results, the FTIR methodology could be developed further to provide semi-quantitative information on the different spodumene forms in the future. This would permit the use of a fast, cost-effective and portable technique for quality control of the spodumene forms, which would open opportunities across the Li value chain. Full article
(This article belongs to the Special Issue Advances in the Geometallurgy of Battery Minerals)
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18 pages, 12444 KiB  
Article
Detailed Microparticle Analyses Providing Process Relevant Chemical and Microtextural Insights into the Black Mass
by Mickaël Dadé, Thomas Wallmach and Odile Laugier
Minerals 2022, 12(2), 119; https://doi.org/10.3390/min12020119 - 20 Jan 2022
Cited by 7 | Viewed by 3528
Abstract
Eramet uses a combination of physical and hydrometallurgical treatment to recycle lithium-ion batteries. Before hydrometallurgical processing, mechanical treatment is applied to recover the Black Mass which contains nickel, cobalt, manganese and lithium as valuable elements as well as graphite, solvent, plastics, aluminium and [...] Read more.
Eramet uses a combination of physical and hydrometallurgical treatment to recycle lithium-ion batteries. Before hydrometallurgical processing, mechanical treatment is applied to recover the Black Mass which contains nickel, cobalt, manganese and lithium as valuable elements as well as graphite, solvent, plastics, aluminium and copper. To evaluate the suitability for hydrometallurgical recycling, it is essential to analyse the Black Mass chemically but also with respect to size, shape and composition of particles in the Black Mass. The Black Mass of various battery recyclers was investigated by using a combination of SEM/QEMSCAN® analyses. This specific QEMSCAN® database contains 260 subgroups, which comprise major and minor chemical variations of phases. The database was created using millions of point analyses. Major observations are: (1) particles can be micro-texturally characterised and classified with respect to chemical element contents; (2) important textural and chemical particle variations exist in the Black Mass from several origins leading to different levels of quality; (3) elements deleterious to hydrometallurgical processing (i.g. Si, Ca, Ti, Al, Cu and others) are present in well liberated particles; (4) components can be quantified and cathodes active material compositions (LCO, different NMC, NCA, LFP, etc.) that are specific for each battery type can be identified; (5) simulation of further physical mineral processing can optimise Black Mass purity in valuable elements. Full article
(This article belongs to the Special Issue Advances in the Geometallurgy of Battery Minerals)
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18 pages, 3046 KiB  
Article
Improving Separation Efficiency in End-of-Life Lithium-Ion Batteries Flotation Using Attrition Pre-Treatment
by Anna Vanderbruggen, Aliza Salces, Alexandra Ferreira, Martin Rudolph and Rodrigo Serna-Guerrero
Minerals 2022, 12(1), 72; https://doi.org/10.3390/min12010072 - 06 Jan 2022
Cited by 37 | Viewed by 6759
Abstract
The comminution of spent lithium-ion batteries (LIBs) produces a powder containing the active cell components, commonly referred to as “black mass.” Recently, froth flotation has been proposed to treat the fine fraction of black mass (<100 µm) as a method to separate anodic [...] Read more.
The comminution of spent lithium-ion batteries (LIBs) produces a powder containing the active cell components, commonly referred to as “black mass.” Recently, froth flotation has been proposed to treat the fine fraction of black mass (<100 µm) as a method to separate anodic graphite particles from cathodic lithium metal oxides (LMOs). So far, pyrolysis has been considered as an effective treatment to remove organic binders in the black mass in preparation for flotation separation. In this work, the flotation performance of a pyrolyzed black mass obtained from an industrial recycling plant was improved by adding a pre-treatment step consisting of mechanical attrition with and without kerosene addition. The LMO recovery in the underflow product increased from 70% to 85% and the graphite recovery remained similar, around 86% recovery in the overflow product. To understand the flotation behavior, the spent black mass from pyrolyzed LIBs was compared to a model black mass, comprising fully liberated LMOs and graphite particles. In addition, ultrafine hydrophilic particles were added to the flotation feed as an entrainment tracer, showing that the LMO recovery in overflow products is a combination of entrainment and true flotation mechanisms. This study highlights that adding kerosene during attrition enhances the emulsification of kerosene, simultaneously increasing its (partial) spread on the LMOs, graphite, and residual binder, with a subsequent reduction in selectivity. Full article
(This article belongs to the Special Issue Advances in the Geometallurgy of Battery Minerals)
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20 pages, 6204 KiB  
Article
Geometallurgical Characterisation with Portable FTIR: Application to Sediment-Hosted Cu-Co Ores
by Quentin Dehaine, Laurens T. Tijsseling, Gavyn K. Rollinson, Mike W. N. Buxton and Hylke J. Glass
Minerals 2022, 12(1), 15; https://doi.org/10.3390/min12010015 - 22 Dec 2021
Cited by 10 | Viewed by 3756
Abstract
Cobalt (Co) mine production primarily originates from the sediment-hosted copper (Cu) deposits of the Democratic Republic of Congo (DRC). These deposits usually consist of three ore zones with a supergene oxide ore blanket overlying a transition zone which grades into a sulphide zone [...] Read more.
Cobalt (Co) mine production primarily originates from the sediment-hosted copper (Cu) deposits of the Democratic Republic of Congo (DRC). These deposits usually consist of three ore zones with a supergene oxide ore blanket overlying a transition zone which grades into a sulphide zone at depth. Each of these zones display a mineral assemblage with varying gangue mineralogy and, most importantly, a distinct state of oxidation of the mineralisation. This has direct implications for Cu and Co extraction during mineral processing as it dictates which processing method is to be used (i.e., leaching vs. flotation) and affects the performance of these. To optimise resource efficiency, reduce technical risks and environmental impacts, comprehensive understanding of variation of ore mineralogy and texture in the deposit is essential. By defining geometallurgical ore types according to their inferred metallurgical behaviour, this information can serve to classify the resources and improve resource management. To obtain insight into the spatial distribution of mineral grades, it is necessary to develop techniques that have the potential to measure rapidly and, preferably, within the mine at relatively low-cost. In this study, the application of portable Fourier transformed infrared (FTIR) spectroscopy is investigated to measure the mineralogy of drill core samples. A set of samples from a sediment-hosted Cu-Co deposit in DRC was selected to test this approach. Results were validated using automated mineralogy (QEMSCAN). Prediction of gangue and target mineral grades from the FTIR spectra was achieved through partial least squares regression (PLS-R) combined with competitive adaptive reweighted sampling (CARS). It is shown that the modal mineralogy obtained from FTIR can be used to classify the ore according to type of mineralisation and gangue mineralogy into geometallurgical ore types. This classification supports selection of a suitable processing route and is likely to affect the overall process performance. Full article
(This article belongs to the Special Issue Advances in the Geometallurgy of Battery Minerals)
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