Calcination scheme NTUA
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.
© visual:Adobe Stock Photos
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.
© visual:Adobe Stock Photos
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.
Register to the Symposium on Direct Lithium Extraction
© visual:EnBW
Europe stands at a turning point in its journey towards establishing a competitive European value chain for batteries. Important steps have been taken in encouraging battery manufacturing plants, only to mention here the inauguration of the first gigafactory by Northvolt in Sweden. Yet, the market demand for batteries continues to surge, fueled not only by the electric vehicle sector but also by other mobility applications and stationary storage needs. The recently launched Quarterly EU Electricity Market Report Q3 ’23 indicates over 600,000 new battery electric vehicles (BEVs) were registered in Q3 ’23, 36% higher than the corresponding quarter in 2022 and counting for 24% market share.
In response to these record demands, the European batteries research and innovation (R&I) community has been dedicated to supporting the establishment of this industrial value chain in Europe, aided by public funding, including by the European Union. Various R&I projects under the umbrella of the BATT4EU Partnership (established under Horizon Europe Programme in 2021), LiCORNE included, are sharing forces within the Cluster Hub “Production of materials for batteries from European resources” to address common challenges.
Motivated by the global geopolitical developments, the strategic role batteries play in achieving Green Deal objectives and the ever-evolving nature of battery technologies, Europe recognises the critical need for strategic alignment among stakeholders. Replacing the BATT4EU SRIA of 2021 and the Batteries Europe SRA of 2020, the 2024 SRIA outlines key strategic actions that the European Batteries R&I Community will undertake to advance collaborative research projects facilitated by the BATT4EU Partnership. Different from the previous strategic agendas, the 2024 roadmap goes beyond specific chemistries, leveraging also the power of disruptive (digital) technologies to advance research across all battery types, including material science, manufacturing and recycling processes.
The new agenda draws on the roadmaps published by Batteries Europe and Battery 2030+, compiling inputs from numerous European battery experts, offering recommendations on short, medium, and long-term objectives. It emphasises the need for coordinated action not only at the European level but also within national and regional programmes.
The 2024 SRIA points to the following six imperatives which are necessary to set the foundations and support a competitive battery value chain in Europe:
• Ensure that (BATT4EU) research results reach gigafactories and the markets, through pilots, demonstrators and improved decision making aided by digital tools.
• Increase the strategic autonomy of Europe by reducing the reliance on foreign critical raw materials by supporting local and circular supply chains and support research into different battery chemistries, including sodium-ion technologies.
• Improve battery affordability to accelerate the green transition and keep the European industry competitive by improving batteries based on materials that are more abundant and pushing for better integration into end-use applications.
• Improve the flexibility of battery manufacturing and recycling systems to reduce lock-in effects and respond quickly to changes in a rapidly developing industry.
• Implement a safe and sustainable by design framework for batteries, which plays to European strengths, and which will help reduce emissions and use of substances of concern, improve safety and allow for the integration of smart functionalities.
• Support the continuity of excellent European battery research and academic-industrial cooperation by improving access to research facilities and pilot lines, use research projects to build up a skilled workface, and by avoiding gaps in research through continued funding, which will bind talented researchers to Europe.
BATT4EU Partnership is organising a webinar on 20 March 2024, between 10:00 and 11:30 Brussels time. The aim is to present the official document and to host engaging discussions with the experts behind this publication who will explain how this document will redefine the dynamics for the European battery sector.
Register here
On Thursday, 16 November, during the 2023 edition of the Raw Materials Week, the twelve EU funded projects that constitute the Cluster Hub ‘Materials for batteries’ gathered for their annual event in Brussels.
The Cluster Hub has been initiated last year during the 7th edition of the Raw Materials Week. The main objective of the meeting was to meet and discuss the latest developments in the participating projects as well as the new challenges and opportunities discovered through the projects’ lifetime. Nader Akil, Operations Manager at PNO Innovation, inaugurated this second edition outlining the motivation behind the hub’s establishment. He underlined the positive reception and sustained interest from various stakeholders keen on joining this initiative.
Discover and/or rediscover the first edition of the Cluster Hub workshop
Co-organised by RELiEF, EXCEED, ENICON and RAWMINA, the event was also the opportunity to welcome the four new members of the Cluster (EXCEED, RAWMINA, METALLICO and CRM-geothermal). the workshop gathered nearly 100 organisations driving the production and the recycling of raw materials for battery applications from primary and secondary resources.
Building on the initial objective of creating an environment that could foster knowledge exchange on different approaches for the recycling and recovery for battery applications, the event focused on three major topics that depict the transversality characterising the projects: the raw materials through research and science, the roles and challenges of industry and market for raw materials, and the raw materials under the scope of sustainability, durability and social acceptance. During this annual meeting, an interactive session led by Anish Patil from TechConcepts and representing the RELiEF project had the objective of Mapping the European battery material recycling landscape – more details to be found below, in the section referring to the interactive session.
The first session was moderated by Sonia Matencio from LEITAT, representing the RAWMINA project. This session had the objective of discussing the raw materials through research and science, under the scopes of mining, refining, processing as well as the battery data. Sonia introduced this topic under the scope of RAWMINA, explaining the integrated innovative pilot system for Critical Raw Materials recovery from mine waste in a circular economy context. To this end, Christophe Aucher, from LEITAT as well, highlighted the need on an open battery passport system to better reflect and account for any adaptations that might be required due to the changing regulatory landscape.
Sonia welcomed afterward Brecht Dewulf from KU LEUVEN and representing ENICON, who discussed the sustainable processing of Europe’s low grade sulphidic and lateritic Ni/Co ores and tailings into battery grade metals. The idea behind this was to show all the potential of Ni/Co resources for Europe.
Xochitl Dominguez from VITO concentrated her speech on gas-diffusion electrocrytallisation (GDEx), a crucial topic for the projects LiCORNE and RHINOCEROS she works with. GDEx is an electrochemical process of reactive precipitation of metals in solution with oxidising or reducing agents produced in-situ by the electrochemical reduction of a gas, in a gas-diffusion electrode. This was followed by Katrin Kieling from GFZ Potsdam, working there for the CRM-geothermal project and shortly explained the challenges of extracting critical raw materials from geothermal fluids. To conclude this first session, Sandra Pavón from Fraunhofer IKTS explained the demonstration of battery metals recovery from primary and secondary resources through a sustainable processing methodology in the METALLICO project.
Discover presentations from Session 1
The annual meeting followed its course with an interactive session led by Anish Patil, which scrutinised stakeholders’ perspectives on the Green Deal Industrial Plan, Net Zero Industrial Act, Critical Raw Materials Act and the European Battery Regulation 2023. Mentimeter facilitated this interactive session, engaging the audience to explore how these policies intersect, complement each other, and identify critical measures and incentives for achieving their objectives.
Over 30 persons participated in the live-poll proposed, which results display the priority to be set on funding and state aid regarding ranking the four pillars of the Green Deal Industrial Plan in order of relevance (followed by skills development, conductive regulation, and open and fair trade). Another major topic regarding the stimulation of investment in net Zero technologies, the majority of answers placed the ‘enhanced skills’ as first priority, shortly followed by facilitating the access to the market.
Lastly, the participants were divided regarding the critical measures to implement in the EU to stimulate investment in building domestic capacities for extraction of critical raw materials (CRMs). Although the majority opted for ‘cutting red-tape and accelerated permitting’, approximately half of the answers evoked uncertainty, which emphasised one more time the need to engage with policy makers as external stakeholders in all projects.
This interactive workshop was followed by two sessions, which aimed at discussing the challenges and opportunities of raw materials within the frame of industry and market, as well as the social acceptance, sustainability, and durability.
Alan Gonzalez from PNO Innovation Begium, representing LiCORNE, moderated the industry part, whereas Sam Hoefman from RELiEF moderated the last session on social acceptance, sustainability, and durability. Distinguished panellists took the stage to engage in debates on various topics.
Edvarts Emerson, Production and Testing Engineer at Watt4Ever, presented his work on the benchmark depository of 2nd life use of lithium in batteries, acceptance criteria and guidelines, work developed within the RHINOCEROS project. Benjamin Wilson, representing the RESPECT Project, displayed Aalto University’s work advancing efficient, sustainable, innovative and safe battery recycling processes in the EU. Laura Kainiemi from LUT University, representing the RELiEF Project, Konstantinos Komnitsas from the Technical University of Crete (TUC), on behalf of EXCEED, and Vitor Correia from INTRAW for the CRM-geothermal project, collectively debated the role and impact of social acceptance among affected communities, the importance of triggering new dialogues on responsible mining activities, and the joint involvement of regional, national and European authorities, academia, industry partners, and citizens in shaping these initiatives.
A big thank you to all participants for this co-creative and very constructive and inspiring meeting.
Discover presentations from Session 2
Discover presentations from Session 3
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.
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