News

Extraction of concentrates, waste cathode material, ore and tailings

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.

Separation and purification of Li from solutions

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.

Recovery as battery-grade chemicals

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

Supply and characterisation of feedstock

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.

Beneficiation and physico-chemical transformation of concentrates

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.

Within the collaborative framework of the Cluster Hub “Production of raw materials for batteries from European resources”, the LiCORNE consortium members had the opportunity to encounter another EU-funded initiative – CRM-geothermal project.

Coordinated by Katrin Kieling (GFZ Potsdam), the CRM-geothermal project shares a mission akin to LiCORNE’s – to alleviate Europe’s need of critical raw materials (CRMs), thus contributing to the energy and digital transition. Attending online, the project coordinator introduced the project’s concept, which focuses on innovative technologies that leverage the combined extraction of CRMs and energy from geothermal fluids. The coordinator emphasised various advantages of the combined heat/electricity extraction, including maximising returns of investment, avoiding additional land occupancy, minimising environmental impact often associated with mining activities.

A distinctive feature of CRM-geothermal is its contribution to the CRMs community through the establishment of the CRM-geothermal Fluid Atlas for Europe and East Africa. This initiative brings innovative aspects such as an AI-based Simulation Tool, utilizing artificial intelligence and machine learning tools to analyse extensive datasets collected over time.

Much like LiCORNE, CRM-geothermal sets a clear commitment to contribute to the domestic CRM supply chain, thus diminishing reliance on imported resources and mitigating risks tied to market and political instabilities. Additionally, it promotes more trustworthy and ethical supply chains for certain CRMs, balancing public resistance to raw material extraction – much needed due to the growing demand for these resources.

Learn more about CRM-geothermal here

Discover the upcoming Cluster Hub annual workshop here.

The most recent political events and regulatory context have highlighted on several occasions a growing demand for lithium (Li), primarily fuelled by the increasing use of lithium-ion batteries (LIBs). The concentration of the largest mining sites for Li outside of Europe leads to a strong dependence on third countries, which can pose economic and strategic challenges for the EU. To mitigate the resources scarcity, the EU has implemented regulations promoting sustainable battery practices, and is actively exploring diversified domestic resources of Li, such as the geothermal brines located in the Rhine Graben region.

Researchers at Fraunhofer ICT recently attended the German Geothermal Conference in Essen (Germany), where they submitted a scientific poster that portrays the characteristics of the Li resources identified in the geothermal brines in the Rhine Graben region and the challenges raised by the Li extraction. Due to the high concentration of salt load, the selective separation of Li and sodium (Na) remains the primary challenge to solve. Within the LiCORNE project, researchers are testing a manganese-based (Mn-based) adsorption setup to provide Li enriched solutions from geothermal brines. Despite recent developments, impurities persist, and additional separation steps are required.

Lithium Extraction from geothermal brine of the Rhine basin by electrophoresis

During the German Geothermal Conference, the research team at Fraunhofer ICT presented the free-flow electrophoresis (FFE) used for the selective separation of Li and Na ions. This separation relies on the ions’ migration velocity in an electrified field, being significantly influenced by their charge, size and hydrate shell.

The main advantage of the FFE lies in its capacity to prevent mixing of individual streams with the background eluent, allowing separate collection of the individual streams at the end of the chamber.  Additional benefits of the FFE:

Testing the method with different parameters, various concentrations of the sample solution and altering the eluent solution, researchers reported a complete separation of Li and Na ions by FFE, with over 80% separation efficiency. Future efforts will focus on testing the actual desorption solutions, optimizing throughput, scaling up, and reducing costs.

Download the original poster, available in German, here

Late September 2023, ministers, industry leaders, investors, international organisations and civil society convened at IEA (International Energy Agency) headquarters for first-of-its-kind summit to discuss the future of critical minerals.

Being the first international IEA Critical Minerals and Clean Energy Summit, the event applauded governments’ enthusiasm to deploy the clean energy transition, as well as their quick actions to ensure secure and sustainable supplies of critical minerals. With a concerning scenario portraying surging demand of minerals such as lithium, cobalt, nickel and copper, driven by the deployment of clean energy technologies, the first international summit identified six key actions to ensure secure, sustainable and reliable supplies of critical materials:

  1. Accelerate progress towards diversified minerals supplies.
  2. Unlock the power of technology and recycling, setting priorities on sustainable extraction and processing technologies and to increase the recycling rates covering all potential streams: e-waste, industry scrap, end-of-life batteries, wind turbines and permanent magnets.
  3. Promote transparency in markets: “The participants emphasised the need to promote transparent markets that facilitate new investments by reinforcing due diligence and traceability practices.”
  4. Enhance the availability of reliable information, with enhances focus on producing public up-to-date data, facilitating decision-making processes among various stakeholders.
  5. Create incentives for sustainable and responsible practices: “rewarding environmental, social and governance (ESG) efforts and speeding up approvals of new facilities without loosening legal and regulatory protections.”
  6. Foster international collaboration.

The majority of these strategic actions are already included in the core of the LiCORNE project. Launched in October 2022, LiCORNE is designed to establish the first European Lithium complete supply chain. Its main objective is to increase the processing and the refining capacity for battery-grade chemicals from resources available in Europe: ores, brines, tailings and off-specification battery cathode materials (waste).

With increased interest for this first international summit, the IEA will hold a Ministerial Meeting next year, in February, which will provide countries with a platform to evaluate the significance of critical minerals in the global energy security and climate action. Based on shared experiences and information, the event will emphasise transparent and resilient supply chain strategies, and unveil the next phase of the IEA Voluntary Critical Mineral Security Programme.

Photo © IEA

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.

Achieving over 95% selective Li recovery from geothermal brines

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. Its lithium, sodium and potassium mining potential faces opposition from indigenous communities and environmental activists.

 

In July 2023, International Energy Agency (IEA) released its inaugural “Critical Minerals Market Review”, along with their new online data explorer. Between 2017 and 2022, the demand of lithium (Li) tripled, primarily due to the energy sector’s reliance on it. According to the report, the market for energy transition minerals is poised for continued rapid growth, placing increasing pressure on the global mining industry.

Looking in particular at the Li price fluctuations, the study reports increases in 2021 and early 2022, accompanied by strong volatility. However, the latter half of 2022 and the beginning of 2023 saw more stable trends, albeit still remaining above historical averages.

Not unexpected, investment in the development of critical minerals, particularly Li, recorded a significant surge of 30% in 2022, building upon a previous increase of 20% in 2021. The IEA analysis examined the investment patterns of 20 major mining companies actively involved in the production of minerals essential for the energy transition. It revealed a substantial rise in capital expenditure specifically allocated to critical minerals. This upward trend can be attributed to the favourable momentum propelling the adoption of clean energy solutions, such as the most recent EU Regulation on Batteries and Waste Batteries. According to the IEA analysis, companies specialising in Li development witnessed 50% rise in their investment spending. Fuelled by the rising demand of electric vehicles, large industrial groups are competing now in a quest to secure mineral supplies: General Motors announced a 650  million USD in Lithium Americas, while Tesla confirmed already plans to build a Li refinery in Texas (USA).

Along with its ‘Critical Minerals Market Review 2023’, the IEA also launched the IEA Critical Minerals Data Explorer, an interactive tool that facilitates access to the agency’s projection data.

LiCORNE Project and EU’s Vision for the Energy Transition

The IEA analysis conclusions raise the concern of the diversity supply. The LiCORNE project was launched at the encounter of European aspirations to advance the energy transition. The project aims to increase the European Lithium (Li) processing and refining capacity to produce battery-grade chemicals from ores, brines and off-specification battery cathode materials. Over a span of 48 months, from the 1st  of October 2022 to the 30th of September 2026, eight research and development centres in Europe will investigate no less than 14 new technologies for extracting, recovering and refining Li.

Currently in its first year, the LiCORNE project completed the task of characterising and providing materials for the R&D activities.  Most of the materials are sourced from European resources, including spodumene and Li-rich mica from mines in France and Austria, and geothermal brine sampled from the Upper Rhine Graben (France and Germany). The synthetic brine is prepared in UK. Only continental brine and off-specification cathode material originate from non-European countries – Chile and Korea.

For more information, refer to the detailed article, and explore the available Li resources in Europe.

On 16 March 2023, the European Commission proposed a comprehensive set of priority actions to ensure the EU’s access to a secure, diversified, affordable and sustainable supply of critical raw materials (CRMs). With the demand for CRMs expected to skyrocket, Europe needs to mitigate the risks associated with the supply chain of strategic minerals, as highlighted by shortages in the aftermath of the Covid-19 and the energy crisis. 

During the official statement, President of the European Commission, Ursula von der Leyen highlighted:  

“This Act will bring us closer to our climate ambitions. It will significantly improve the refining, processing and recycling of critical raw materials here in Europe. Raw materials are vital for manufacturing key technologies for our twin transition – like wind power generation, hydrogen storage or batteries. And we’re strengthening our cooperation with reliable trading partners globally to reduce the EU’s current dependencies on just one or a few countries. It’s in our mutual interest to ramp up production in a sustainable manner and at the same time ensure the highest level of diversification of supply chains for our European businesses.” 

What is new?

In addition to an updated list of critical raw materials, the Act presents a set of clear benchmarks for domestic capacities along the strategic raw material supply chain, and to diversity EU supply by 2030: 

Other take-aways relevant to the LiCORNE project and the entire Li supply chain

Eurometaux’s immediate reaction, openly stated by the Director General Guy Thiran, emphasised : “Europe has a meaningful project pipeline for the mining, processing and recycling of base metals, battery materials, and rare earths (inside and outside its territory). These can be brought online by 2030 under the right conditions, adding to Europe’s existing production with the same guarantee of high climate and environmental performance. 

Although the proposed Regulation needs to pass the European Parliament‘s and the Council of the European Union’s evaluations before adoption and entry into force, the initiative sets a clear regulatory framework to support the development and the sustainable exploitation of domestic Li resources.   

Read the official press release

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 

Reactive milling and aqueous leaching of waste and cathode material

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

XRD patterns of the MC processed cathode waste materials with Al and Ca as reducing agents