XRD patterns of the MC processed cathode waste materials with Al and Ca as reducing agents
On 12 December 2024, the third edition of the annual workshop of the Cluster Hub “Production of Raw Materials for Batteries from European Resources” took place in Brussels, being co-organised by EU-funded projects RHINOCEROS, CRM-geothermal and CICERO. This third edition, along with an increasing number membership, confirm the hub’s role as a dynamic ecosystem that continues to generate innovations in the European battery materials sector.
The hub’s annual workshop, held as a satellite event of the Raw Materials Week 2024, provided once again a platform for presenting the most promising results from participating projects. Two technical sessions covered the entire battery value chain, from raw materials mining to recycling, while the opening conveniently portrayed the policy, the regulatory and strategic frameworks that support and drive the EU R&I initiatives in the battery sector.
Susana Xara, Project adviser on raw materials at European Health and Digital Executive Agency (HaDEA), established the discussions tone, navigating through the insights of the Critical Raw Materials Act [CRMA] and the Net Zero Industry Act [NZIA] and focusing on their contribution to securing a sustainable supply of critical raw materials for the European battery industry.
Wouter IJzermans, BEPA Executive Director, presented the long-term vision and potential revisions of their roadmap, emphasising the importance of policy frameworks and incentives in promoting battery innovation and deployment across Europe.
The presentation of Vasileios Rizos from the Centre for European Policy Studies (CEPS) identified various barriers and challenges emerging from the EU policy framework on batteries, based on inputs from 20 companies across the entire battery value chain, including partners from the BATRAW project, member of the Cluster Hub since 2022. The representative of CEPS concluded with a set of policy messages referring to early dialogue channels established between policy-makers and various stakeholders. Before the legal requirements entry into force, this information exchange on availability of secondary data sets could enable stakeholders to assess the data quality, select suitable sets of information and identify potential data gaps.
Publicly available resources submitted by CEPS:
Orchestrating the launch and on-going work of the Cluster Hub, PNO Innovation Belgium [part of PNO Group – leader in innovation and funding consultancy], represented by Dr. Nader Akil, concluded the first session with an overview of all EU funding programmes supporting research, innovation and investment in raw materials production for batteries. Additional to the upcoming funding opportunities and guidance on selecting the appropriate funding opportunities based on the status of technology, Dr. Nader Akil introduced another initiative launched by PNO Group – DIAMONDS4IF. This project supports the preparation of Innovation Fund applications, enabling the transfer of H2020 research results into successful ventures and securing investment funding.
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The session of technical presentations debuted with RAWMINA project, represented by Carmen Estepa, R&D Manager at AGQ Mining & Bioenergy, providing an overview of its final results on the demonstration activities of an integrated innovative pilot system for CRMs recovery from mine wastes. Up-to-date results indicate encouraging extraction rates of ~90 % Fe, ~95 % Co and ~60 % antimony (Sb) yielded by the bioleaching process. Additionally, the alkaline leaching applied after bioleaching extracted more than 90 % tungsten (W), while the following processing step – Fe precipitation, confirmed that Fe and Sb can be removed almost completely from the solution (>90 %). Finally, the processes engaged in the selective CRM recovery yielded promising recovery rates in the range of 99 % for Co, 65 % for W, 77 % for Sb.
Dr. Albert Genter, Deputy General Manager of ES Géothermie, presented the geochemical characterisation of geothermal reservoir rocks in the Upper Rhine Graben – results of their activities conducted within the LiCORNE EU-funded project. After a short incursion into the geological formation of the Upper Rhine Graben (URG) area, Dr. Albert Genter highlighted the feasibility of lithium (Li) extraction from the geothermal brines. The high Li concentrations in the geothermal brine at Soultz-sous-Forêts and Rittershoffen [in the range of 150-200 mg/L], combined with significant water flows exploited by the geothermal power plants, indicate a great potential for Li production in the URG. After establishing the fluid circulation within the fractures of the geological formation, the research team at ES-G will continue investigating the chemical composition of sedimentary rocks, which are also part of the reservoir Soultz-sous-Forêts, and conducting Li and strontium (Sr) isotope analyses to provide more detailed information about the origin of lithium in the brine.
Dr. Nivea Magalhães [Univ. of Exeter, UK] presented the conclusions of the forensic geometallurgy protocol established within the ENICON project. Often, information not directly related to processing leads to limited insights into ore processing behaviour. ENICON investigates the impact of mineral textures and grain size on liberation, sometimes interfering with automated mineralogy results. Additionally, the project presented the findings of the ore characterisation of the Kevitsa mine, containing nickel (Ni)- and cobalt (Co)-bearing minerals.
The CRM-geothermal presentation, delivered by Saskia Bindschedler, Professor at Univ. de Neuchatel, Faculty of science, Institute of biology, Laboratory of microbiology, focused on the use of microbial activity for Li recovery from geothermal brines. Geothermal brines are characterised by high temperatures, increased pressure and salinity, conditions favourable for bioextraction processes using microbes. Key findings confirmed the feasibility of microbial-driven processes for Li recovery, enabling effective filtering of elements using oxalate compounds, followed by precipitation via oxalothropic bacteria, such as Pandoraea sp.. While the researchers will continue working on oxalotrophy and initial pH optimisation, focusing on improving the scalability, they will additionally investigate Li concentration in fluid samples.
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An insight into the results of the METALLICO project, with focus on their COOL+ technology, was delivered by Sandra Pavon from Fraunhofer IKTS. COOL+ is one of the five technologies investigated within the framework of METALLICO, that involves a leaching step using supercritical CO2, that enables the extraction of Li in a more efficient and environmentally friendly manner. After explaining the five phases of the process and comparing the results at the main conclusions reported high selectivity and efficiency in Li recovery, achieving Li2CO3 which meets battery-grade specifications with a purity of 99.7 %. The solid silicate residue that remains after the CO2 leaching step is not wasted. Instead, it is repurposed to produce geopolymers which are further used in the construction sector, aligning with the principles of circular economy and zero-waste.
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On 16 October 2024, the Karlsruhe Institute of Technology (KIT) was hosting not only the LiCORNE project’s M24 consortium meeting, but also its first exploitation workshop. The event brought together a diverse group of stakeholders, with nearly 15 industry guests and members of the External Advisory Board (EAB), to discuss the latest advancements in lithium (Li) extraction technologies.
The workshop began with a welcome address by Dr. Lourdes Yurramendi [the coordinator of the LiCORNE initiative and Project Director at TECNALIA Waste Valorisation, Energy, Climate and Urban Transition], followed by Nader Akil, Operations Manager at PNO Innovation Belgium, who outlines the objectives of the exploitation workshop and provided an overview of the LiCORNE project. Funded by the European Commission, the project aims to develop competitive technologies for Li extraction and recovery from various feedstocks, including ores, geothermal brines and cathode waste materials. Following this introduction, various partners delivered technical presentations, showcasing their innovative approaches and key exploitable results after 24 months from the start of the project.
Regardless the feedstock considered, all these novel technologies share one theme: sustainability. This focus on sustainability translates into exploring research routes that go beyond the current state-of-the-art (SoA), reducing energy and water consumption and the generation of chemical waste:
Beyond technological presentations, the workshop also facilitated discussions with external participants, including members of the EAB and industry representatives. These exchanges provided valuable insights into the industry’s needs and opened up new routes for collaboration. To facilitate future collaborations, PNO presented several funding opportunities that can be used to bring the most promising technologies and the LiCORNE selected flowsheet to a pilot level.
As the project progresses, the focus will shift now towards the benchmarking and selection of the most promising LiCORNE technologies for upscaling to produce ~1 kg of battery-grade Li by the end of the project. This phase aims to shape a path towards larger piloting and future commercialisation.
With no surprise, after Europe’s quest to replace fossil fuels and turn towards clean energy, lithium (Li) has been classified as a key component, making it to the short list of EU’s highly significant critical raw materials. With the transition to zero-emission vehicles, carmakers, as the most consuming industrial sector, will need ever more Li for batteries.
Renowned for its policy background, the EU decisional institutions adopted the Critical Raw Materials Act (CRMA) in record time. This accelerated adoption procedure shows nothing but the need for action, which reflects Europe’s urge to secure a sustainable supply of critical raw materials (CRMs). The CRMA sets specific targets to strengthen the EU’s capacities along the different stages of the value chain, ensuring that by 2030:
Both EnBW and LevertonHELM are key partners in the LiCORNE project. EnBW, as one of the largest energy supply companies in Germany and Europe, has the following tasks in the LiCORNE project: 1) to supply geothermal brine feedstock, respectively to conduct develop Li+ desorption technology aiming at min. 90% yield from geothermal and continental brines. LevertonHELM, on the other side, is a Lithium chemicals producer based in the UK, focusing on the manufacturing of a wide range of inorganic Li chemicals. In the framework of LiCORNE, the British company will benchmark and qualify the Li produced by the processes developed in the project, as battery-grade material.
German, respectively British companies have expanded their collaboration beyond the project’s framework, with a joint objective to advance the sustainable production of battery-grade Li carbonate and Li hydroxide – essential materials for electric mobility and energy storage solutions.
In previous articles, EnBW reported high Li concentrations for the geothermal brines in the Upper Rhine Valley (Bruchsal reservoir), ranging from 163 to 190 mg/L (Sanjuan et al., 2016). However, due to the characteristics of the reservoir, featuring highly mineralised brines, the extraction process was hampered by an elevated additional concentration of foreign ions (TDS 130 g/l). According to Laura Herrmann, Project Manager Research and Development at EnBW, the process requires increased selective adsorption technology in line with the exigences of the battery materials producers.
This industrial collaboration has resulted in a remarkable purity of 99.5% for lithium carbonate, demonstrating great potential for further scale-up to meet the EU’s demand for lithium.
Using direct Li extraction by adsorption (A-DLE), the process coordinated by the industrial partnership led to a remarkable purity of 99.5 % for Li carbonate. This successful initial trial holds promise for future upscale, potentially meeting the EU’s demand for Li.
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© visual:EnBW
The European energy transition will be built on electrification, relying on clean technologies highly depending on metals, the majority being listed as critical and strategic raw materials. JRC’s Foresight Study, assessing supply chain dependencies and predicting materials demand until 2050, highlights EU’s need to diversity and secure a more resilient resourcing of needed metals. Additional recommendations refer to the necessity to explore Europe’s potential to build internal capacities for mining, refining and processing materials needed for battery production.
In the coming years, demand for lithium-ion batteries (LIBs) will be driven by the automotive sector, complemented by the demand for energy storage systems (ESS) storage requested by the deployment of renewables. Compared to the current supply of materials, major increases are foreseen for graphite (45% in 2030 and 85% in 2050) and lithium (Li) (100% in 2030, expected to reach 170% in 2050). In 2030, the cobalt (Co) demand for batteries will represent almost 60% of the current world supply, expecting to decrease to 40% in 2050, partly due to the shift towards more nickel-rich batteries [source: Foresight Study, JRC].
In the current scenario, overshadowed by geopolitical instability and reliance on powerful nations for critical minerals, the recently adopted Critical Raw Materials Act (CRMA) underpins, among other solutions, the need to turn towards domestically sourced recycled metal, which will help reduce reliance on imports or single sources. With clear objectives to strengthen EU’s capacities along the entire value chain, the CRMA additionally sets a threshold for the EU’s processing capacity, which should cover by 2030 at least 40% of the domestic annual consumption of strategic materials.
Researchers from SINTEF have been studying the possibility of recovering Li, nickel (Ni) and Co from secondary raw materials such as black mass, as well as Li from primary resources – spodumene concentrate. The team at SINTEF approached the task by converting the metals in raw materials using molten salt chlorination, a process that could become an alternative to state-of-the-art (SoA) hydrometallurgy.
Researchers conducted experiments on three types of input materials: one spodumene concentrate and two different samples of black mass (BM), the first one of unknown battery chemistry and pre-treatment, while the second BM sample, recovered from an NMC material, had undergone pyrolysis pre-treatment.
The experiments allowed researchers to study the thermal expansion and melting behaviour of the spodumene concentrate, obtaining the highest Li yield (100 %) when chlorine gas is used in a mixture of calcium chloride, sodium chloride and potassium chloride at a temperature of 727 ⁰C . Experiments on black mass material showed the highest chlorination yields were obtained from uncalcined material (Li 64 %, Co and Ni 22-24 %, Cu 83% and Mn 49 %) in a mixture of lithium chloride and potassium chloride at at 470 ⁰C.
The results of this research was presented by SINTEF representatives at the Joint Symposium on Molten Salts in November 2023.
Discover the scientific publication
© visual: SINTEF
Author: ADMIRIS [ADM]
ADMIRIS [ADM], partner in WP9 [Communication, Dissemination and Exploitation] and responsible for designing and proposing a sound business model for the LiCORNE project, successfully delivered the preliminary market and logistics analysis. This initial study marks an essential milestone in the journey towards understanding the optimal LiCORNE value chain and is the first step in a series of three reports designed to reach the project’s final business analysis.
The scope of this preliminary analysis was extensive, focusing on understanding the dynamics of the market through supply-demand analysis, pricing evaluations, and logistics assessments. Delving into these key areas allowed researchers to gain valuable insights that would facilitate the selection of the most suitable locations for the LiCORNE plant facilities. The study examined the external dynamics of lithium products, thus identifying market trends, challenges, and opportunities. This comprehensive picture of the market landscape will allow partners to pinpoint optimal plant locations that align with the project’s strategic objectives.
Main take-aways from this preliminary study:
The results of this preliminary analysis are promising, showcasing several potential plant locations that offer favourable conditions for the LiCORNE technologies within Europe. These findings pave the way for further exploration and refinement as we progress towards our ultimate goal of establishing a robust and efficient Li value chain.
In advancing the development of LiCORNE’s business case, the consortium partners remain committed to leveraging these insights to drive the success of this project that has the potential to revolutionise the lithium industry and deliver innovative solutions to meet the growing demands of the market.
© Photo: Minakryn Ruslan (under Adobe License)
Using alkaline leaching process on spodumene concentrate, the maximum extraction of Li achieved thus far reached 75%. The leachate transformation, even after the filtration step, hinders the sample analysis and further processing. To overcome this challenge, upcoming experiments will explore elevated temperatures, diverse additives, and further investigate the chemical precipitation process.
During the advanced solvometallurgy applied on spodumene concentrate, the research team at TECNALIA reported high Li leaching yields (>95%). Their future work will focus on the further optimisation of the operational conditions, more appropriate for the anticipated scalability phases of the process. On the other hand, solvometallurgical tests carried on waste cathode material achieved high leaching yields for all target elements (Li, Co, Ni, Mn) using mild operational parameters.
After the first experiments engaging reactive milling and aqueous leaching [treated with aluminium- (Al) and calcium (Ca) – salts] on waste cathode material, researchers at KIT reported close to 31% Li recovery rate. Samples supplied by UMICORE were leached under different conditions to extract Li – available in the form of Li carbonate [LiCO3], and further subjected to purifications processes employing various reducing agents. Future efforts for this particular task will focus on adjusting leaching temperatures, establishing an optimal purification process, and evaluating Li recoverability in both Al and Ca systems.
Anticipating future upscaling phases, researchers at VITO, working on the Li-sieve adsorption and desorption from aqueous leachates, shaped the lithium-titanium-oxide (LTO) adsorbents into spheres, which enabled dynamic testing. The team is currently optimising the flow rates for adsorption and desorption to model the optimal conditions for upcoming processes. While initial tests utilised synthetic Li solutions, upcoming research will extend to purification processes for spodumene leachates.
In the same work package, TECNALIA performed experiments using different organic solvents for the liquid/liquid (L/L) extraction from brines showing promising Li yields in the range of 40-60 %.
Within the same work package, EnBW scientific team has been working on designing an eco-friendly Li-desorption process from brines, focusing on the development of novel synthesis for Mn-based adsorbent material. Notably, the successful upscaling of the synthesis process from 2,5g to 200g marks a significant achievement in sustainable material synthesis.
Finally, the last task of WP5 – Electrode-based Li adsorption and desorption from brines, conducted by KIT, presented the conclusions of their research work carried during the last six months, which includes a 4-step process. Their work has been focusing recently on the optimisation of the electrode pre-treatment, the establishment of the current densities and the reduction of the Na contaminations. Despite high Li selectivity rates obtained thus far, their work in the upcoming months will centre around optimising the recovery efficiency and the selectivity. Future experiments will test different thermal operating conditions (40°, 60°, 80°), but will also attempt to scale-up the process.
In the final technical work package, SINTEF scientists are pioneering a two-step process which involves in a primary phase selective chlorination by converting insoluble oxides to soluble chlorides; this is followed by a second step – electrolysis of the soluble chlorides extracting the target elements. After conducting different chlorination experiments, researchers emphasised the importance of time and the processing duration, confirming over 65 % Li recovery rate. With promising results, their focus pivots towards the second step – electrolysis.
Read the next article for a comprehensive overview of the meeting.
Marking the project’s first anniversary, the LiCORNE partners gathered in sunny city of Athens to draw the line and brief on the progress achieved thus far. The meeting was hosted by the National Technical University of Athens (NTUA) and it unfolded over two days, including also a visit of the NTUA mineralogical museum and its metallurgy laboratory facilities.
Press the “play” button below to watch snippets of the 1-year consortium meeting and interviews with various partners
Starting with work package (WP) 2, partners from EnBW presented the characteristics of the Bruchsal geothermal reservoir, located at the eastern edge of Upper Rhine Valley. EnBW highlighted that geothermal brines in the Upper Rhine Valley are recognised for their relatively high lithium (Li) concentrations. Additionally, the region displays an extension structure striking in the NNE-SSW direction, with a length of around 300 km and a width of up to 40 km. In this area, the deep geothermal fluids utilised for geothermal applications exhibit a maximum Li concentration ranging from 163 to 190 mg/L (Sanjuan et al., 2016). The highest Li concentration was detected in the hydrothermal alteration zone of Lower Buntsandstein.
In the forthcoming months, new samples are prepared for delivery to research partners: geothermal and continental brines, but also Li-phosphate samples, a new Li-mica concentrate and synthetic brine solutions. Upcoming research will mainly focus on the geochemical analysis of rock samples from the reservoirs.
In the mining industry or extractive metallurgy, beneficiation is any process which removes the gangue minerals from ore to produce a higher-grade product, and a waste stream – which, despite the lack of valuable materials, needs to be sustainably treated. In charge of the beneficiation step, TU Delft already presented in M12 videos of the operational opto-magnetically-induced sorting lab setup to process crushed spodumene ore. This proof of concept aims to separate the Li-rich fractions of the ore before reaching the metallurgical processes. This preliminary step helps improve efficiencies and decrease cost in processes downstream.
Researchers at NTUA, working on the development of a calcination technology working at lower temperatures, presented the first results of their investigations using various additive combinations and leaching experiments studying the effect of temperature, time and leaching agents. Tests showed that the use of additives has the potential to maintain the calcination operating temperature of spodumene at low temperatures compared to conventional routes. Moreover, researchers achieved over 92 % Li extraction during various leaching experiments conducted so far. Recognising the environmental footprint associated with the conventional routes used for Li extraction, NTUA research team will continue experimenting with new additives in order to develop a new technology that is more environmentally sustainable and equally more competitive.
Working with spodumene samples, TECNALIA researchers have been working on the ball milling-assisted chemical transformation, testing the use of various additives and experimenting with different thermal treatments. Their upcoming work will focus on optimising the ball milling process to obtain materials with similar leaching properties but being produced with less intense thermal processes.
Read the next article for a complete overview of all the work packages.
Lithium (Li), a highly versatile element, finds extensive applications in diverse industries including ceramics, glass, fuel cells, metallurgy, pharmaceuticals, aerospace, and lithium-ion batteries (LIBs). With the demand of LIBs increasing, particularly fueled by portable electronics and electric vehicles, the global lithium industry is undergoing rapid expansion. Due to its lightweight and reactive properties, Li is considered the essential component in high-energy-density batteries, playing a crucial role in the future of sustainable energy. But the extraction of Li resources has become a critical concern.
VITO employs an innovative process known as Gas-Diffusion Electrocrystallisation (GDEx) technology to achieve the direct extraction of Li, that leverages gas-diffusion electrodes to orchestrate a meticulously controlled chemical transformation. By precisely manipulating its parameters, GDEx enables synthesis with minimal chemical additives, marking a significant milestone in this field. The unique design of the reactor maintains a consistent set of conditions, and by simply altering the inlet solution, it can produce the desired target structure. This approach is highly scalable and promising for the future of Li extraction and synthesis.
Following comprehensive investigations performed on synthetic solutions, VITO fine-tuned the operational parameters to be applicable to natural brine solutions and leachates. The experiments carried out on diverse brine solutions yielded remarkable results, with a Li removal efficiency exceeding 95% from these solutions. The planned process involves producing layered double hydroxide structures which can further be downstreamed to battery cathode material.
Learn more about the GDEx process in the previous article: Recovery as battery-grade chemicals
©Adobe Stock Photos, Salinas Grandes, a huge salt flat in Jujuy and Salta, Argentina.
VITO achieves direct lithium extraction, using the Gas-Diffusion Electrocrystallisation (GDEx) technology. GDEx uses gas-diffusion electrodes to achieve this goal, by producing in-situ the necessary quantities of mild chemicals, which in turn form precipitates containing lithium.
During this period, the GDEx team has conducted experiments with synthetic solutions. The effect of adding chemical supplements to the process is being investigated to optimise the lithium recovery yield and selectivity vs. competing ions in solution. After optimising the GDEx process with synthetic streams and learning about the precipitating mechanisms, we are looking forward to extending the process in various geothermal brine solutions obtained from the consortium partners. After precipitation in the form of layered-double hydroxides, the GDEx team will investigate the downstream steps to obtain battery-grade lithium hydroxide.
More information about the GDEx process can be found at http://gdex.vito.be
Focusing on mechanochemical (MC) processing, the recovery of high-value components from the cathode waste supplied by UMICORE is planned to be performed within Task 4.3.
The ball milling process of waste cathode material was optimised at laboratory scale using different reducing agents such as Al, Ca, and their mixtures. The role of the MC conditions (ball-to-sample ratio (B/S), ball milling time, and nature of the reducing material) was further investigated and analysed. This showed the kinetics of the MC-induced reduction reaction is sensitive to multiple processing parameters.
After the reduction reaction, the powder X-ray diffraction (XRD) analysis revealed the formation of metallic composites and Al/or Ca oxides, as illustrated in the figure below. The upcoming research will be dedicated to investigating and optimising the aqueous leaching conditions of the ball-milled samples at laboratory scale.
XRD patterns of the MC processed cathode waste materials with Al and Ca as reducing agents