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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)

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.

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.

 

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

Between 14 and 18 November 2022, the European Commission organised the 7th edition of the Raw Materials Week gathering a wide range of stakeholders discussing policies but also relevant alternatives in the field of raw materials. This was an opportune occasion for the LiCORNE project to cluster with seven other EU-funded projects at the event “Production of raw materials for batteries from European sources”. The objective of the workshop was to create an environment that could foster knowledge exchange on different approaches for the recycling and recovery for battery applications. Co-organised by CROCODILERHINOCEROS and LICORNE, with the participation of the EU funded projects BATRAWRESPECTRELiEFFREE4LIB and ENICON, the workshop gathered nearly 100 organisations driving the production and the recycling of raw materials for battery applications from primary and secondary resources.

Due to the increasing usage of batteries for electric vehicles (EVs) and energy storage systems generated by the EU’s mission to limit climate change, the demand for many metals relevant for batteries is expected to grow by more than 1000% by 2050. Held in a hybrid format, the workshop provided participants with the opportunity to discover innovation routes followed by the clustering projects on their pathway to secure sustainable and responsible sourcing of raw materials for battery production.

Nearly three hours packed with presentations provided stakeholders with essential information about each project, from the main objectives and expected outcomes, to the lessons drawn from the activities carried out.

The CROCODILE project – First of a kind commercial Compact system for the efficient Recovery of Cobalt Designed with novel Integrated Leading technologies– was presented by Dr. Lourdes Yurramendi (TECNALIA). As the most mature project, CROCODILE’s keynote focused on valuable findings and learnings regarding different aspects of the project: the samples treatment, the selection of flowsheets, the life cycle analysis (LCA) and cost (LCC) of the pilot unit, to name only a few.  Later on Monday, the project was also featured as a Success Story in the Raw Materials Week, where the presentation video was played for the first time.

Download the CROCODILE presentation

Sonia Matencio Lloberas (LEITAT) presented the BATRAW project – Recycling of end-of-life battery packs for domestic raw material supply chains and enhanced circular economy. This project will develop and demonstrate two innovative pilot systems for sustainable recycling and end-of-life (EoL)  management of EV batteries. Depending on the results obtained, these technologies could be extended to other types of batteries to recover all the metals and materials contained: i.e., cobalt, nickel, manganese, lithium, graphite, aluminium, and copper.

Download the BATRAW presentation

Nader Akil (PNO Innovation Belgium) explained the mission and the motivation behind the RHINOCEROS project – Batteries reuse and direct production of high performances cathodic and anodic materials and other raw materials from batteries recycling using low cost and environmentally friendly technologies. As attractive energy storage technologies, Lithium-ion batteries (LIBs) have proven to be a reliable solution, especially when it comes to the production of low-emission fleets (EVs), followed by stationary storage market and consumer electronics. According to the Strategic research Agenda for Batteries, by 2030, the global demand for LIBs is estimated to increase 14 times and the EU could account for 17%. The battery market is expected to reach 250 billion EUR/year by 2025, while the production in Europe is foreseen to rise to 300 GWh/year as of 2030. This generates opportunities for projects like RHINOCEROS to develop economically and environmentally viable routes for re-using and recycling EoL EVs and stationary energy storage Lithium-ion batteries (LIBs).

Download the RHINOCEROS presentation

Similar to the RHINOCEROS project, FREE4LIB [Feasible recovery of critical raw materials through a new circular ecosystem for a Li-ion battery cross-value chain in Europe] aims to simplify the recycling process of LIBs, as a more resilient and environmentally friendly alternative to the current linear economic model – take, make, dispose. The project, presented by Juan Castro (CARTIF), will develop six technologies at TRL5 to achieve new sustainable and efficient processes to recycle EoL LIBs: dismantling, pre-treatment and four materials recovery processes aiming to reach highly efficient materials recovery (metal oxides, metals and polymers). Additional to the recycling solutions, FREE4LIB will also target three processes dealing with metals and polymers re-using and electrode synthesis to re-manufacture new LIBs.

Download the FREE4LIB presentation

Justo Garcia (Orano Mining) presented the RESPECT project. Funded by the Horizon Europe research and innovation  programme, the project aims to strengthen expertise in techniques and the value chain for the recycling of electric vehicle batteries at European level. The RESPECT project will develop a global process encompassing a process-chain flexible enough to treat all kinds of batteries in closed loop. Precisely, researchers will explore two recycling routes: full hydrometallurgy and direct recycling, and an improved Life Cycle Assessment of each recycling segment to reduce emissions, health risks and safety issues.

Download the RESPECT presentation

Recently launched, the LiCORNE project – Lithium recovery and battery-grade materials production from European resources, was introduced by Alan González Morales (PNO Innovation Belgium), who explained briefly the project’s ambitious objectives to establish the first-ever Li supply chain in Europe. With five large primary resource owners (including one of the world leaders in Li production) involved in the consortium, the project aims to increase European Li processing and refining capacity for producing battery-grade chemicals from ores, geothermal and continental brines, tailings and off specification battery cathode materials (waste).

Download the LiCORNE presentation

Gabriel Hidalgo, from the Recycling Unit of Avesta Battery & Energy Engineering (ABEE), outlined the objectives and the impact expected from the RELiEF project – Recycling of Lithium from Secondary Raw Materials and Further. Expected to boost the recycling industry, this project aims to reduce Li waste by more than 70%, and to transform recycled resources into high value battery-grade material. Relying on a very diversified consortium, RELiEF will additionally propose a new business model for materials acquisition and processing, taking into consideration environmental and social sustainability.

Download the RELiEF presentation

Sofía Riaño Torres (KU LEUVEN) presented the last EU project, ENICON– Sustainable processing of Europe’s low-grade sulphidic and lateritic nickel/cobalt ores and tailings into battery-grade metals -Launched in June 2022, the project aims to improve the refining capacity of domestic and imported low-grade Ni/Co. ENICON’s metal recovery route using hydrochloric acid dispenses with the old-school hydro-based approach that involves continuously precipitating and redissolving metals. Thus, it reduces the amount of chemicals needed for metal dissolution, which results in the production of potentially harmful waste streams. More information about the project in the joint documentary commissioned together with EU funded project NEMO: Responsible Mining in Europe.

Download the ENICON presentation

The workshop in figures

Although only in its first edition, the clustering workshop Production of raw materials for batteries from European resources attracted a diversified range of stakeholders. Counting more than 150 people registered, the audience was dominated by research organisations (26,97%), the rest of the audience being equally distributed between academia (17,76%), large companies (17,11%), SMEs (16,45%), EU institutions (4,61%) and other stakeholders addressing raw materials – national and regional administrative authorities, logistics service provides, investing companies, trade associations, NGOs, consulting companies (17,76%). Participants are located mainly in Europe but a percentage of nearly 20% shows growing enthusiasm from third countries, such as Turkey, Canada, South Korea, Chile, etc.

Exploring future clustering ideas

With the real peak of valuable outcomes from H2020 projects coming now, the aim goes beyond informing about the progress achieved to date. Building on the knowledge generated so far, new projects need to address different challenges, such as the high cost of exploration activities, the geological uncertainty, and the necessity to develop improved processing and refining technologies for better recovery of minerals and metals from side streams and industrial waste. Such challenges require close collaboration on all levels and across the entire battery value chain.

The last part of the event featured an interactive session, which included seven questions scrutinising stakeholders’ interest for similar clustering initiatives. With favourable answers and reviews, the Production of raw materials for batteries from European resources could turn into a permanent clustering hub fostering knowledge exchange and stimulating synergies between projects. More information will follow soon.

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