Author: KIT

Following previous work performed in work package 5, researchers from KIT further investigated the lithium (Li) extraction from black mass (BM) supplied by partners ACCUREC (ACC) and TES.

The BM provided by ACC consists of graphite, as well as transition metals such as nickel (Ni), manganese (Mn), and cobalt (Co), along with their respective oxides and impurities like copper (Cu), iron (Fe) and few fluorinated compounds. Li is present in the form of lithium carbonate (Li₂CO₃), lithium fluoride (LiF) and lithium aluminium oxide (LiAlO₂). However, breaking off lithium aluminium oxide to a soluble Li-salt and removing fluoride contamination proved to be challenging.

Previous work reported the simultaneous incorporation of fluoride ions and decomposition of LiAlO₂ using an excess of calcium hydroxide (Ca(OH)₂) at elevated temperatures.  More recent developments of the processes show improvement, especially decreasing considerably the amount of of Ca(OH)₂ , while achieving a Li extraction of 87 %. Instead of heating the suspension, it is possible to initiate the reaction by liquid-assisted grinding in a planetary mill. The results show LiAlO₂ is decomposed. However, the fluoride content is not efficiently removed.

In the BM supplied by the partner TES, most Li is present as lithium transition metal oxides (LiTMO) and a small amount of LiF. To enable Li extraction, this BM was reduced by reactive milling in Task 4.4 – Reactive milling for the production of metallic black mass (MBM). The obtained MBM consists of graphite, the metallic composite, lithium oxide and the oxidised reducing agent, along with some impurities like Fe and fluorinated compounds.

After investigating aluminium (Al) and calcium (Ca) in the previous steps, researchers at KIT performed tests to assess Li extraction using a magnesium (Mg) system, which presents various advantages, namely: avoiding, on one hand, the formation of Li salts with bad solubility, and relying on the other hand on insolubility of Mg in the high pH aqueous solution.

After aqueous extraction, researchers obtained a mixture of Li₂CO₃ and LiF. In the upcoming months, this mixture will be purified to a battery-grade material.

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, marking the last step in the decision-making procedure.

Looking back in time, less than three years ago, the raw materials was a topic exclusively tackled by ‘connaisseurs’. Today, it has become a strategic file, and the speed of its adoption shows need for action 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 a threefold objective: to increase and diversify the EU’s CRMs supply, to strengthen circularity, including recycling, and to support research and innovation (R&I) on resource efficiency and the development of substitutes. 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].

Read the official press release

Echoing the official communication, Commission Vice-President Valdis Dombrovskis declared for Euractiv: “Trade flows of critical raw materials are highly concentrated,” adding, “While we will continue to rely on imports, we need to massively diversify.”

The official document sets a threshold of 65% of the EU’s annual consumption of any CRM deriving from any single country. The CRMA establishes also a list of 34 critical and no less than 17 strategic raw materials considered crucial for the twin green and digital transition, as well as for defence and space industries.

In addition to the updated list of CRMs, the act introduces three targets for annual consumption of raw materials:

• 10% for local extraction
• 40% EU domestic processing threshold
• 25% of supply emanating from recycled material

These changes modifying the recycling target reflect the increasing importance of paving a circular economy model that ensures a sustainable supply of raw materials.

© visual: European Commission

Authors: CHA and PNO

An important component of a Li-ion battery (LiB), the electrolyte has a crucial role in the cell performance. The nonaqueous electrolyte is a multicomponent system consisting of a conductive salt, mainly LiPF₆ (Lithium hexafluorophosphate – inorganic component), organic carbonate solvents and additives.

Numerous research initiatives are dedicated to the design of the electrolyte composition, aiming to optimized performance, increased safety, lifetime and streamlined costs. However, once a LiB reaches its end-of-life (EoL) stages, the electrolyte receives less attention in the favour of the valuable metals that can be recycled from the cathode: Li, Co, Mn, Ni, Al, Cu. Moreover, due to its volatility, toxicity and high flammability, the electrolyte recycling is less studied. When ignored, the spent electrolyte reacts with water to form fluoride, leading to its uncontrolled decomposition and/or evaporation, and thus generating an imminent environmental risk. Due to its composition that includes organic solvents, the presence of residual electrolyte in the black mass is considered hazardous, and it is often a reason hampering the recycling process.

Researchers at Chalmers University (CHA) ) developed a sub- and supercritical carbon dioxide (sc-CO₂) extraction process to selectively recover the electrolyte from spent LiBs. Sc-CO₂ extraction technologies are already widely employed in the food, beverage, pharmaceutical, and cosmetic industry. In a nutshell, sc-CO₂ forms when CO₂ surpasses its critical point at 31°C and 73.8 bar pressure. In this so-called supercritical state, CO₂ demonstrates optimal mass-transfer characteristics and can be fine-tuned to alter its physicochemical characteristics by adjusting pressure and/or temperature. However, CO2 proves ineffective as a solvent for high molecular weight polymers and highly polar ionic compounds. However, the addition of a co-solvent or a modifier can significantly improve the solubility properties of sc-CO₂, making this alternative a suitable process to selectively extract LiPF₆ after solvent removal.

Researchers at CHA investigated different process parameters (pressure, temperature, extraction times) to understand their impact on the extraction behavior of different electrolyte solvents such as ethylene carbonate. Their analysis included both qualitative and quantitative results indicating the composition and the purity. Simultaneously, the research also monitored the process exhaust stream for potential formation of LiPF₆ decomposition products. The findings showed that that the non-polar electrolyte solvents like dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate were successfully extracted using low-density CO₂. The more polar electrolyte components such as ethylene carbonate and propylene carbonate were stepwise extracted by gradually increasing the system’s pressure. The developed technology is a game changer not only for electrolyte recycling but also for increased workplace and transportation safety due to removal of the flammable and hazardous substances from battery black mass. The simplicity of the processing design is an additional advantage of the technology.

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© Photo credit: Adobe

During the past years, the increase in the use of lithium-ion batteries (LIBs) has become more prominent. An unsurprising trend, whatsoever, due to the widespread and rapid adoption of clean mobility applications, electronic devices, and energy storage systems. Despite their undeniable environmental and social benefits, several challenges lie ahead. In 2022, global lithium demand exceeded the supply despite an 180% increase, IEA reports. Recent communications already forecast the demand of lithium (Li) is expected to soar over the next decade, with mobility accounting for the main consuming market.

The current supply of primary resources is deemed insufficient for the growing demand. Approximately 60% of today’s lithium is mined for battery-related applications, a figure that could reach 95 percent by 2030, McKinsey reports estimate. But this rapid increase in the use of LIBs in EVs will introduce a large quantity of spent batteries in the near future. The alternatives to manage spent batteries include remanufacturing, repurposing and recycling, with the latter one playing a significant role from both ecologic and economic points of view.

Current recycling processes lack selectivity in recovery control and require significant consumption of reagents and energy. The research conducted by the RHINOCEROS partners at Sapienza University of Rome (UoS), Department of Chemistry, aims to develop an electrochemical process for selective extraction of Li from electrodic powder of end-of-life (EoL) LIBs. This concept simulates the charging process of a LIB with an aqueous electrolyte and a cathode material (counter electrode) that facilitates water reduction. The hydroxyls freed by water reduction and the Li + cations deintercalated by the anode will form a LiOH solution.

Using two samples – a commercial powder, respectively one coming from EoL LIBs, and testing the delithiation process using various parametres, UoS researchers obtained:

• Li extraction of 99% from commercial powder
• Li extraction of 82% from waste powder

The lower Li extraction on EoL electrode powders compared to commercial ones is due to the presence of SuperP [a high purity and structured carbon black powder with a moderate surface area for the lithium-ion industry], which oxidises under delithiation conditions.

Discover the scientific publication

Between 14 and 18 November 2022, the European Commission organised the 7^th 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 RHINOCEROS 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 CROCODILE, RHINOCEROS and LICORNE, with the participation of the EU funded projects BATRAW, RESPECT, RELiEF, FREE4LIB 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.

The Cluster Hub “Production of raw materials for batteries from European resources”

After the successful workshop held in November 2022, the participating projects launched in January the cluster hub  carrying the same title – “Production of raw materials for batteries from European resources”. The platform is a collaboration-driven community sharing the same mission – to foster the knowledge necessary to drive a more sustainable and circular production of raw materials for the European battery industry.

Join the hub

 

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