Periodic Reporting for period 1 - CICERO (MSA-based circular hydrometallurgy for sustainable, cost-effective production of NMC cathode materials)
Período documentado: 2023-11-01 hasta 2025-04-30
On 23 May 2024 the Critical Raw Materials Act (CRMA) entered into force in the European Union to ensure a diverse and sustainable supply of critical raw materials for the EU's industry. Secured access to critical raw materials is essential for strategic sectors including clean technologies, digital, defence and aerospace industries.
By targeting the domestic refining of three “strategic” battery- related CRMs, i.e. Ni, Co and Mn, the CICERO project addresses the one if the CRMA benchmark’s: i.e. > 40% domestic processing/ refining. To tackle the twin problems of (1) Europe’s dependence on a few third countries (i.e. DRC, Indonesia, China) for the supply of Ni, Co and Mn for our NMC Li-ion battery production, and (2) the fact that these metals are currently produced at a huge cost in terms of environment, health and safety, CICERO puts in place a sustainable, cost-effective refining model for Ni, Co and Mn, and the downstream conversion into “made-in-Europe” NMC cathodes. The CICERO project is the first ever to develop a circular hydrometallurgical Ni, Co & Mn processing/refining scheme that uses methanesulphonic acid (MSA) – a commercial, green, REACH-compliant & affordable acid – rather than H2SO4. CICERO recovers, refines and converts Ni, Co and Mn from domestically available secondary raw materials: (a) post-mining raw materials (sulphide & laterite tailings) and (b) Ni/Co/Mn-bearing intermediates incl. MSP, FeNi, Ni-matte and Mn-anode sludge.
To achieve this, CICERO develops a suite of novel metallurgical unit processes for advanced MSA leaching and solution purification, the conversion to battery-grade MSA salts, and the synthesis of NMC cathodes in MSA media, with sound reagent regeneration & iron recovery in line with the Twelve Principles of Circular Hydrometallurgy.
By targeting the domestic refining of three “strategic” battery- related CRMs, i.e. Ni, Co and Mn, the CICERO project addresses the one if the CRMA benchmark’s: i.e. > 40% domestic processing/ refining. To tackle the twin problems of (1) Europe’s dependence on a few third countries (i.e. DRC, Indonesia, China) for the supply of Ni, Co and Mn for our NMC Li-ion battery production, and (2) the fact that these metals are currently produced at a huge cost in terms of environment, health and safety, CICERO puts in place a sustainable, cost-effective refining model for Ni, Co and Mn, and the downstream conversion into “made-in-Europe” NMC cathodes. The CICERO project is the first ever to develop a circular hydrometallurgical Ni, Co & Mn processing/refining scheme that uses methanesulphonic acid (MSA) – a commercial, green, REACH-compliant & affordable acid – rather than H2SO4. CICERO recovers, refines and converts Ni, Co and Mn from domestically available secondary raw materials: (a) post-mining raw materials (sulphide & laterite tailings) and (b) Ni/Co/Mn-bearing intermediates incl. MSP, FeNi, Ni-matte and Mn-anode sludge.
To achieve this, CICERO develops a suite of novel metallurgical unit processes for advanced MSA leaching and solution purification, the conversion to battery-grade MSA salts, and the synthesis of NMC cathodes in MSA media, with sound reagent regeneration & iron recovery in line with the Twelve Principles of Circular Hydrometallurgy.
CICERO’s Ni/Co/Mn-bearing (a) low-grade post-mining raw materials and (b) distinct intermediates were characterized.
Novel bioleaching approaches to pre-concentrate Ni, Co and Mn from the Kevitsa and Luikonlahti sulphidic tailings were developed.
High elution percentages of Ni, Co and Mn were obtained with MSA when using bioleachate of laterite tailings;
Tailored MSA-leaching processes were developed for Mn sludge and MHP. The other Ni/Co/Mn-bearing intermediates were not suited for leaching with MSA. Upscaling is the next step.
Electrocoagulation tests have shown promising pH adjustment and Fe removal, but the >99% Fe removal target has not yet been consistently met under high metal loadings. Further optimization is ongoing to support integration with downstream processes targeting battery-grade Ni, Co, and Mn salts. Considering the initial results, further tests will be done to address the effectiveness of hollow fibre impregnated membrane.
Solubility of MSA salts in different MSA-solutions were determined and a public report on the solubility & dissolution enthalpies of MSA salts as a function of T was produced.
The electrochemical responses of pure MSA, Ni(MSA)2 and Co(MSA)2 solutions have been investigated in a 3-electrode electrochemical lab-cell with a low concentration of metal ions (0.05 mol/L) and a better understanding of the system has been obtained. Ni and Co metals were deposited in small quantities.
Three promising antisolvents have been identified. Solubility data have been determined for the respective mixed solvent systems involving Ni, Co, and Mn methane sulfonate salts respectively. Antisolvent crystallization processes have been investigated for the respective pure systems using synthetic solutions.
The eutectic freeze crystallization (EFC) setup has been built and tested in the lab. Cooling crystallization experiments have been conducted and solid phases obtained in the low temperature range have been characterized.
Based on synthetic solutions the extraction system was optimised and already tested for one the Mn sludge leachate.
3-compartment BMED setup with Fumatech membranes has been tested in bench scale with Na-MSA and Na2SO4 feeds. The work will continue with optimizing the 3-compartment BMED, testing 2-compartment BMED setup and another supplier’s membranes to reach the current efficiency of 70 %.
Novel bioleaching approaches to pre-concentrate Ni, Co and Mn from the Kevitsa and Luikonlahti sulphidic tailings were developed.
High elution percentages of Ni, Co and Mn were obtained with MSA when using bioleachate of laterite tailings;
Tailored MSA-leaching processes were developed for Mn sludge and MHP. The other Ni/Co/Mn-bearing intermediates were not suited for leaching with MSA. Upscaling is the next step.
Electrocoagulation tests have shown promising pH adjustment and Fe removal, but the >99% Fe removal target has not yet been consistently met under high metal loadings. Further optimization is ongoing to support integration with downstream processes targeting battery-grade Ni, Co, and Mn salts. Considering the initial results, further tests will be done to address the effectiveness of hollow fibre impregnated membrane.
Solubility of MSA salts in different MSA-solutions were determined and a public report on the solubility & dissolution enthalpies of MSA salts as a function of T was produced.
The electrochemical responses of pure MSA, Ni(MSA)2 and Co(MSA)2 solutions have been investigated in a 3-electrode electrochemical lab-cell with a low concentration of metal ions (0.05 mol/L) and a better understanding of the system has been obtained. Ni and Co metals were deposited in small quantities.
Three promising antisolvents have been identified. Solubility data have been determined for the respective mixed solvent systems involving Ni, Co, and Mn methane sulfonate salts respectively. Antisolvent crystallization processes have been investigated for the respective pure systems using synthetic solutions.
The eutectic freeze crystallization (EFC) setup has been built and tested in the lab. Cooling crystallization experiments have been conducted and solid phases obtained in the low temperature range have been characterized.
Based on synthetic solutions the extraction system was optimised and already tested for one the Mn sludge leachate.
3-compartment BMED setup with Fumatech membranes has been tested in bench scale with Na-MSA and Na2SO4 feeds. The work will continue with optimizing the 3-compartment BMED, testing 2-compartment BMED setup and another supplier’s membranes to reach the current efficiency of 70 %.
It is early at this stage of the project implementation.