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.

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

RHINOCEROS attending Shifting Economy Week

From 21 to 25 November 2023, the city of Brussels hosted the Shifting Economy Week, an annual event dedicated to showcasing transformative projects that aim to pave the way to an economy that is low-carbon, regenerative, and equally circular. The 2023 exhibitors’ line-up included, among other regional stakeholders, our partner Watt4Ever (W4E), industrial partner specialised in the development of innovative solutions for energy storage and management. W4E leveraged its presence at Shifting Economy Week to to raise awareness about the importance of circular economy principles in the context of the battery industry.

During the same event, W4E’s CEO, Aimilios Orfanos, was invited to speak at the BeCircular conference, an event dedicated to presenting concrete examples of circular economy approaches put in place by Brussels-based companies. He shared insights from W4E’s experience in developing second-life battery systems for electric vehicles, emphasising their potential benefits in terms of environmental impact and cost savings. Simultaneously, the CEO also highlighted the challenges faced by the industry in implementing circular business models, including regulatory barriers and market incentives.

RHINOCEROS at its second participation at Circular Wallonia Days

A few days after attending Shifting Economy Week, W4E represented the RHINOCEROS project at the Circular Wallonia Days, held on 13 and 14 December 2023. Centred around advancing the circularity of the batteries value chain, the event brought together stakeholders from academia, industry, and government to discuss strategies for improving the sustainability of battery production, use, and disposal. The focus topics covered recycling technologies, supply chain transparency, and policy measures to support the transition to a circular battery economy.

© Photo credits: Watt4Ever

On Monday, 10 July 2023, the Council of the European Union adopted a new regulation that strengthens sustainability rules for batteries and waste batteries. This regulation covers the entire life cycle of batteries, ensuring their safety, sustainability and competitiveness from production to reuse and recycling.

Read the official press release

Recognising the vital role batteries play in the decarbonisation process and the transition towards zero-emission mobility, Teresa Ribera, Spanish Minister for the Ecological Transition reinforced the Presidency’s commitment to supporting comprehensive regulation encompassing all types of batteries. This includes waste portable batteries, electric vehicle batteries, industrial batteries, starting, lightning and ignition (SLI) batteries primarily used in vehicles and machinery, as well as batteries for light means of transport like electric bikes, e-mopeds, and e-scooters.

“At the same time end-of-life batteries contain many valuable resources and we must be able to reuse those critical raw materials instead of relying on third countries for supplies. The new rules will promote the competitiveness of European industry and ensure new batteries are sustainable and contribute to the green transition.”

| Teresa Ribera, Spanish Minister for the Ecological Transition

To foster a circular economy, the regulation establishes requirements for the end-of-life phase, including collection targets and obligations, material recovery targets, and extended producer responsibility. Dedicated collection objectives for waste batteries used in light means of transport will be implemented, aiming at 51% by the end of 2028, respectively 61% by the end of 2031. Furthermore, the regulation sets mandatory minimum levels of recycled content for industrial batteries, SLI batteries and electric vehicle batteries. The following initial values have been established:

• 16% for cobalt
• 85% for lead
• 6% for lithium
• 6% for nickel

Additionally, batteries will also be required to hold documentation proving their recycled content.

To improve the functioning of the internal market for batteries and ensure fair competition, the regulation introduces safety, sustainability, and labelling requirements. It includes provisions for battery labelling and information disclosure, including details on battery components and recycled content. Additionally, an electronic “battery passport” and a QR code will be implemented to enhance traceability and transparency. These labelling requirements will take effect by 2026, while the QR code implementation is expected by 2027, providing member states and manufacturers with ample time to prepare.

This new regulation aims to mitigate environmental and social impacts throughout the battery’s life cycle. By establishing strict due diligence rules for operators, the EU is ensuring operators are bound to verify the source of raw materials used for batteries placed on the market. However, the regulation provides for an exemption for SMEs from the due diligence rules.

After its signature by the Council and the European parliament, the new regulation will be published in the EU’s Official Journal, expecting to enter into force 20 days after.

RHINOCEROS project in the current legislative framework

Launched in 2022, the RHINOCEROS project fits within the current framework recently adopted by the Council of Europe under the Spanish Presidency. Designed to support the raw materials supply, the RHINOCEROS project will demonstrate a smart sorting and dismantling robot at TRL6, enabling the automation of a battery repurposing production line. When direct reuse and repurposing of batteries is not possible, RHINOCEROS will investigate several ground-breaking circular recycling routes aiming at the recovery of all materials present in LIBs (e.g., metals, graphite, fluorinated compounds, electrolytes, polymers, and active materials).

A first set of conclusions stemming from the research of our partners generated a database and the parameters for module selection, which will further facilitate the development of electric vehicles 2nd life batteries.

Read more in the article “Acceptance criteria and guidelines for 2nd life prone LIBs” 

The infographic can be accessed on the Council of the European Union’s website using this link.

Aiming towards a zero-waste strategy for the recovery of metals from battery refining waste waters, LEITAT is working on the development and evaluation of novel polymer inclusion membranes (PIM). PIMs are a type of liquid membrane in which the liquid phase, the extractant, is held within a polymeric network. The interest in these membranes has been growing exponentially over the past few years as an alternative separation technique to conventional solvent extraction. 

Work during the first six months has focused on the evaluation of different extractants for the target metals: lithium, manganese, cobalt and nickel. Researchers established a liquid-liquid extraction protocol based on two different processes in which the target metal is extracted and recovered separately. During the extraction step, a specific carrier compound selective towards the target metal separates an amount of it from a feed metal solution. The recovery of the metal takes place in the second process, where a stripping solution is employed to recover the metal previously extracted through the carrier. Initial PIMs containing the most efficient extractants have been prepared, characterised and are currently evaluated. The featured image depicts the continuous procedure used to test the synthesised PIMs.

The current industrial pre-treatment and downstream processes (e.g., pyrolysis, calcination, etc.) are still inefficient and have significant limitations. Plastics and electrolytes sacrificed in the initial stages of the recycling process are overlooked when it comes to their recovery. Within the RHINOCEROS project, Chalmers University [CHA] is working on recycling of ignored content of the LIBs waste, electrolyte and polymeric materials by developing an innovative process based on Supercritical Carbon Dioxide (sc-CO₂) technology. 

Due to its environmental friendliness, non-toxic, low cost and straightforward processing features, the sc-CO₂ technology has been attracting both scientific and industrial interest. With consistent leverage over other processes, sc-CO₂ technology is already widely used in various industries including food, cosmetic and pharmaceutical industries [i.e., to decaffeinate coffee or tea, extract vegetable oils etc.] Although it has many applications, its use in battery recycling was recently discovered and the Chalmers research group is one of the pioneers in this field. 

Within the project’s framework, CHA researchers are targeting the development of the sc-CO2 extraction process which will selectively recycle the electrolyte and the polymeric material from the LiB waste. The electrolyte, binder, and separator will be recycled in subsequent steps and purified to reuse in the battery industry. For this purpose, several critical process parameters such as pressure and temperature are investigated to achieve high recycling efficiencies under feasible conditions. 

Electrolyte recovery

The electrolyte in the LiB is a complex system usually composed of a conductive salt dissolved in a matrix of various solvents and additives. The most recent results reported by CHA on sub- and sc-CO₂ research show that at low pressure and temperature conditions, the non-polar electrolyte components (almost 66% of the electrolyte) were selectively recovered without the generation of toxic gas emissions, which are typically generated by thermal recovery processes originated by the decomposition of the thermally unstable conductive salt.

In this recycling step, the polar electrolyte components are left in the sample as residues and a subsequent recycling step using suitable cosolvent is required for their selective extraction. During the upcoming phases, researchers will aim to recover the electrolyte completely, including conductive salt and solvents. 

In this recycling step, the polar electrolyte components are left in the sample as residues and a subsequent recycling step using suitable cosolvent is required for their selective extraction. During the upcoming phases, researchers will aim to recover the electrolyte completely, including conductive salt and solvents. 

The selection of the co-solvent is critically important not only for effective recycling but also for the sustainability and the feasibility of the developed processes. To assess the suitability of the sc-CO₂ process, its environmental impact and economic competitiveness, CHA researchers explored also other solvents, which allowed them to select the most promising candidates for future research.  

In the upcoming months, CHA will study the effects of co-solvent modified sc-CO₂ system parameters on the recycling efficiency of PVDF and the structural properties of the recycled material. Researchers will carry out intensive characterisation studies to clarify the changes in the material structure, to determine the quality, and to optimise the process to reach the reusability goal. 

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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