ioana.pristavu@pnoconsultants.com, Author at LiCORNE

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.

Policy perspectives and supporting mechanisms for the battery sector

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.

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.

Sustainable sourcing practices for battery materials from primary sources

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.

LiCORNE project presenting the feasibility of lithium extraction from geothermal brines

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.

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 Li₂CO₃which 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.

Research partners from the LiCORNE consortium are working on developing and optimising various technologies to produce battery-grade materials. SINTEF, for instance, have designed, built and tested their advanced electrodialysis apparatus using purified lithium (Li) solutions derived from the upstream treatment processes of Li-ore. Intermediary results show the process will require further optimisation to obtain 99 % purity LiOH and the targeted energy consumption of less than 15 kWh/kg. The research is still ongoing, focusing now on removing the Al ions prior to the electrodialysis process and on investigating new operating parameters.

In another task, working on the optimisation of the conditions for selective chlorination of spodumene concentrate and cathode waste, SINTEF achieved almost 95 % Li yield using CaCl₂-NaCl -KCl melts. Optimisation is underway to replicate the results to the other valuable materials available in the cathode material.

Researchers at TEC have been optimising the organic-based membrane electrolysis process to recover Li from organic solutions as Li₂CO₃. Results indicate they managed to achieve over 95 % Li yield from off-specification cathode material, while recovering all the organic solvent used in the previous (leaching) step for its reuse. Good yield rates have also been obtained for the treatment of solutions produced in the liquid/liquid [L/L] extraction of brines and spodumene. However, the selectivity of the membrane is insufficient to overcome the migration of the high concentration of other competing cations such as Na, K, Mg and Ca. Researchers are currently producing and testing new PIMs (Polymer Inclusion Membranes) to try to improve the results.

The research group at VITO have been refining their gas-diffusion electrocrystallisation process for Li recovery from brines, achieving over 95 % removal of Li from most of the samples. By manipulating and adding salts to the brine sample, results show that more than 99 % Li is extracted. The energy efficiency of the GDEx process can be improved with the optimisation of the GDEx reactor.

With all technological processes reporting progress and reaching the targets established at proposal stage, future months will rely on the results of the LCA and LCC analysis, which will establish the most promising processes that will enter the upscaling phase.

Partners working on various extraction processes of lithium (Li) from a variety of feedstocks – concentrates, waste cathode material, ore and tailings, are reaching target recovery rates.

NTUA researchers have developed an alkaline leaching process to extract Li from spodumene concentrates, which yielded extraction rates of over 92 % and low impurities. The same process, this time applied on lithic mica, resulted in Li extraction rates of nearly 100 % at a longer leaching duration. Moreover, the optimal settings showed the capacity to maintain the level of impurities low. Leaching experiments on mica samples will continue, but results are already encouraging. This new leaching process requires temperatures considerably lower than the conventional extraction process, currently at 1100°C.

Alkaline leaching scheme to extract lithium NTUA

On their side, researchers at TEC have been optimising the solvometallurgical process to extract valuable elements from four type of materials: spodumene concentrates, lithic mica, lithium phosphate and off specification cathode material. After achieving their target of more than 95 % Li extraction from spodumene, the optimisation phase tested (taking advantage of the result from the novel pre-treatment established and previously described) milder leaching conditions, obtaining similar good results. For lithic mica and lithium phosphates, best operations routes investigated have shown that pre-treatment increases considerably the leaching yield at values higher than the target. For the off-specification cathode material, researchers have concluded that mechanical activation of the cake obtained after leaching improves Li extraction, achieving up to 99 % Li recovery and very high selectivity at room temperature processing. Ni, Co and Mn can be separated as a valuable mixture in the same process.

Finally, the research team at KIT, in charge of the reactive milling and aqueous leaching of waste cathode material [NMC], optimised the purification processes using various reducing agents. The intermediary results yielded Li recovery rates ranging between 68,8 % and 91 %, depending on the reducing agent utilised during the purification process. Next steps for KIT research group expand to calculating the lithium carbonate [Li₂CO₃] purity, determining the recovery rate of Ni, Mn and Co and upscaling the ball-milling.

Separation and purification of lithium from solutions

VITO researchers, 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 optimised flow rates and settings initially modelled on synthetic Li solutions have been recently tested on real samples, yielding approx. 85 % Li recovery from aqueous alkaline spodumene leachates. The team at VITO has recently filed a patent application with the desorption stability results.

Expected results have already been shaping up in Spain, where TEC is working on the Li extraction from both continental and geothermal brines. After running tests using the most suitable extractants for their liquid-liquid extraction process [L-L] coupled with stripping operations, researchers have managed to obtain a global Li extraction of 92 % from continental brine, far beyond the initial target of 85 %, while diminishing the content of the accompanying cations (Na, K, Ca and Mg). On the other hand, the same technological process applied to spodumene yields a global recovery rate around >90 % after optimisation of the scenarios based on McCabe-Thiele diagrams.

In another European region, famous for its geothermal resources, EnBW researchers have been investigating Li-extraction from brines. They developed a novel synthesis route for Lithium Manganese Oxide [LMO] adsorbent, for which a patent has been recently filed. The LMO adsorbents have been demonstrating high absorption capacity and selectivity for Li extraction from brines with high salt contents. Offering improved chemical stability and potential for large-scale production of the material, this solution looks very promising for future implementation at industrial level for Li recovery.

Another extraction process, the electrode-based Li adsorption and desorption from brines, has been optimised by KIT. Following the principles of a salt water battery, the electrochemical extractions with Li-selective electrodes yielded encouraging results for the Li-extraction from geothermal brines. The Li selectivity in the recovery solution were in the range of 77 % to 82 %, displaying a good separation from the main contaminants.

Within the beneficiation process, the research group at TUD developed an opto-magnetically induced sorting technology. Within the next months, their work will continue developing their code to optimise the colour identification of target metals, and simultaneously on various set-ups to improve the magnetic attraction and and to ensure the seamless integration of all components of their opto-magnetically induced sorter.

Within the same work package, researchers at NTUA have developed a new calcination technology with additives, tested on spodumene concentrates. Using different settings and parameters, such as the processing temperature, reaction time, pressure, the extraction yields for Li ranged between 71 % and 96 %. Depending on the additive type, adjusting the calcination parameters accordingly can significantly reduce impurities, such as aluminum (Al), present in spodumene concentrate. Simultaneously, NTUA partners have been optimising a new technology for Li extraction with calcination from lithic mica and the results will be available in the upcoming communications.

Calcination scheme NTUA

Working on spodumene concentrates, the research group at TEC has established a novel pre-treatment process that allows a relevant improvement in the next leaching process of lithium for its valorisation. As a result of this method, which includes ball milling combined with additive, the transformation of the mineralogical structure of the spodumene takes place at a significantly reduced temperature, ranging from 1100ºC to 900ºC. Based on these findings, TEC has applied a similar approach for the lithium phosphate and the lithic mica materials, reporting good results.

During the M24 consortium meeting held in Karlsruhe (GER), the project team presented the latest progress achieved in the work package dedicated to the supply and characterisation of the feedstock, with a primary focus on the geochemical analysis of geothermal brines and rocks.

Between M18 and M24, researchers collected and sent for analyses geothermal brine from the reservoir at Soultz-sous-Forêts in France. This latest analysis not only revealed a Li concentration above 170 mg/L, which confirms the stability and the quality of this resource for a potential future lithium extraction in the Upper Rhine Graben geothermal brine.

In addition to brine analysis, the researchers conducted thorough geochemical analyses on core samples from three deep wells in Soultz-sous-Forêts. These wells intersect the Muschelkalk limestone, Buntsandstein sandstone and Visean granite formations. A total of 57 core samples, sourced from depths ranging between 841 to 5060 m were selected for analysis. The focus was on 36 granite samples, where the lithium concentrations varied significantly. According to the analysis of the research team at ES-G, Li concentrations tend to be highly impacted by hydrothermal alteration. They found that Li concentration can vary by two orders of magnitude when compared to the fresh granite mainly due to secondary minerals precipitation. However, solubilisation of Li is identified in most of the case where hydrothermal alteration is important.

Stakeholders interested in the characterisation performed by ES-G have the chance to find more detailed information at the upcoming Stanford Geothermal Workshop, taking place between 10 and 12 February 2025.

Further isotopic analysis of Li and Sr in rock samples will allow researchers to further understand the sources and mobilisation of Li in geothermal brines. These analyses will provide more accurate insights into the geochemical processes involved and support the development of more efficient and sustainable lithium extraction methods.

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.

Lithium’s role in the quest to facilitate the transition to zero-emission industry

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:

Research and industry – hand-in-hand to demonstrate sustainable production of cathode materials for batteries from geothermal resources

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.

EnBW and LevertonHELM produce Li carbonate for the first time from geothermal brine in Germany

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.

Curious to learn more about the Direct Lithium Extraction technologies developed and tested in LiCORNE?

Meeting future demands for sustainable strategic metals recovery and domestic production

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.

SINTEF researchers exploring molten salt chlorination for metal recovery

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.

The Critical Raw Materials Act (CRMA), proposed by the European Commission in March 2023, was adopted by the Council one year later, on 18 March 2024, after Parliament’s first reading, marking the last step in the decision-making procedure. Several years ago, the raw materials topic was a subject addressed mainly by a limited list of “connaisseurs”. This story looks completely different today, when we are referring to the Critical raw Materials Act as a strategic file. The quick adoption procedure shows nothing but the need for action translating Europe’s urge to secure a sustainable supply of critical raw materials (CRMs).

Standing at the core of the Green Deal Industrial Plan, together with the Net Zero Industry Act and the Reform of the electricity market design, the CRMA is a flagship initiative with the following specific objectives:

The bloc further consolidated this timely adoption with a set of complementary regulations and diplomatic initiatives, outlining a clear position ready to reduce reliance on third countries through export restrictions and screening for foreign direct investment across various sectors [e.g. forging strategic agreements with Chile, Greenland, Ukraine, Canada, Rwanda, and more recently Norway and Kazakhstan].

Echoing the official communication, Jo Brouns, Flemish Minister for Economy, Innovation, Work, Social Economy and Agriculture declared: With the Critical Raw Materials Act we want to turn the challenges of our dependencies into strategic autonomy and an opportunity for our economy. This legislative act will boost our mining sector, enhance our recycling and processing capacities, create local and good quality jobs, and ensure that our industry is up and ready for the digital and green transitions.

The CRMs act establishes a lists of 16 ‘strategic raw materials’ (SRMs) and 34 CRMs. The list of CRMs was prepared by the Commission based on their economic importance and supply risk. SRMs were identified based on their relevance for the green and digital transition, as well as for defence and space applications. Additionally, the act introduces for the first time the concept of “Strategic projects” which would be eligible for streamlined permitting processes and easier access to financing, with provisions aiming to speed up the permit granting process for critical raw material projects.

On 6 May 2024, the Regulation was published in the Official Journal, marking its entry into force.

Among European geothermal sites, the Upper Rhine Graben (URG) has a great potential for a lithium (Li) production from geothermal brines due to its high concentration and the significant water flows exploited by the geothermal power plants in this area.

Despite its great potential, certain gaps in the basic knowledge of the geochemistry of the URG rocks are persisting, as there is scarce conclusive investigation carried out in the past to estimate the Li content as well as the mechanisms of Li recharge in brine. Identifying Li-rich geological units are essential to target areas with higher Li concentrations for exploration and to ensure the sustainability of this resource.

In geothermal systems, hydrothermal fluids circulate through the fractured and porous rock formations, undergoing complex interactions with the surrounding lithology. Various processes, such as leaching, dissolution, and precipitation, can occur and they can significantly influence the concentration of Li in the circulating fluids. Knowing the chemistry of the reservoir rocks could help us understand chemical reactions occurring between the hydrothermal fluids and the rocks and therefore how Li is mobilised and transported into the geothermal brine.

In the LiCORNE project, ESG is conducting detailed geochemical analysis of several core drills including granite, sandstone, and limestone from geothermal wells drilled in Northern Alsace. Researchers finalised the rock sampling task at the beginning of 2024, while the chemical measurements are expected at the end of June, current year.

AN ES-Geothermie employee sampling of granite rocks in the core shelter.

In total, 57 samples were collected and closely studied, which facilitates understanding of the chemical elements behaviour in the rock before and after the hydrothermal circulation/alteration. Comparing the results of this on-going investigation with the few data available in literature and referring to the Li concentration in URG rocks could reveal an unexpected behaviour of Li in the geothermal reservoir rocks.

After careful analysis of the chemical composition, isotopic analysis of the same rock will follow which will show more accurately potential sources of Li in the geothermal brine.

A. Fresh monzogranite sampled at 1774.5 m depth); B. Hydrothermally altered granite showing argillic alteration sampled at 2159.30 m depth. © ES-Géothermie (ESG)

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