Rare Metal Extraction & Processing: Li, Co, Ni
Sponsored by: TMS Extraction and Processing Division, TMS: Hydrometallurgy and Electrometallurgy Committee
Program Organizers: Gisele Azimi, University of Toronto; Takanari Ouchi, University of Tokyo; Kerstin Forsberg, KTH Royal Institute of Technology; Hojong Kim, Pennsylvania State University; Shafiq Alam, University of Saskatchewan; Alafara Baba, University of Ilorin; Neale Neelameggham, IND LLC
Monday 8:30 AM
March 15, 2021
Room: RM 44
Location: TMS2021 Virtual
8:30 AM
Introductory Comments: Rare Metal Extraction & Processing: Gisele Azimi1; 1University of Toronto
Introductory Comments
8:35 AM Keynote
Scenarios of Future Lithium Use, 2021-2040: Roderick Eggert1; 1Colorado School of Mines
For the foreseeable future, lithium-ion batteries appear to be the preferred energy storage technology for electric vehicles (EVs); so this use of lithium will depend importantly on rates of EV deployment and the type of EV deployed. For stationary energy storage associated with wind and solar power, however, the preferred storage technology is less certain. Finally, there are non-battery uses for lithium that are important to consider. This paper compares and contrasts plausible alternative scenarios of future lithium use.
8:55 AM Invited
The Importance of Spodumene Decrepitation on the Lithium Sulfate Extraction: Colin Dessemond1; Gervais Soucy1; 1Université de Sherbrooke
Since lithium-rich minerals regained market shares, spodumene has become one of the most important sources of lithium worldwide. Its theoretical Li content of 8 wt% and the specific thermal treatment and lithium extraction process known since 1950 make it a perfect candidate for industrial projects. However, it has been proven that the known α and β forms are not the only ones involved in this process. An elusive third phase, γ-spodumene, exists and is a non-negligible phase of the spodumene system. This phase has been specifically studied to determine that it has a metastable character that can be shown via thermodynamic calculations, that it is formed regardless of temperature treatment up to 1050°C and finally that it has a significantly negative impact on lithium extraction from 10 wt% and above. Therefore, γ-spodumene can not be ignored when processing α-spodumene as it can lead to decreased lithium extraction efficiencies.
9:15 AM
Application of Eutectic Freeze Crystallization in Recycling of Li-ion Batteries: Yiqian Ma1; Michael Svärd1; James Gardner1; Richard Olsson1; Kerstin Forsberg1; 1KTH - Royal Institute of Technology
The widespread and increasing use of Li-ion batteries has led to an impending need for recycling solutions. Consequently, recycling of spent Li-ion batteries with energy-efficient, environmentally sustainable strategies has become a research hotspot. In this work, eutectic freeze crystallization (EFC), which requires less energy input than conventional evaporative crystallization (EC), has been investigated as a method for recovery of Ni and Co sulfates from synthetic acidic strip solution. Two binary sulfate systems have been studied. Batch EFC experiments have been conducted. It is shown that, with suitable control of supersaturation, ice and salt crystals can be recovered as separate phases below the eutectic temperatures. The work shows that EFC is a promising alternative to EC for the recovery of Ni and Co sulfates from spent Li-ion batteries.
9:35 AM Invited
Selective Separation of Co and Ni from REE in Recycling: Gulaim Seisenbaeva1; Ani Vardanyan2; 1 Swedish University of Agricultural Sciences; 2 Swedish University of Agricultural Sciences
A series of solid silica nanoparticles and mesoporous microparticles were prepared by sol-gel method. They were modified by specific organic functions bearing N- and S-donor ligands with enhanced affinity to late transition metals. The materials were characterized by TGA, SEM-EDS, AFM, XRD, FTIR and potentiometric titration. The adsorption kinetics and thermodynamics for Co(II) and Ni(II) cations was investigated. Selectivity of uptake for later transition metals in relation to rare earth elements was tested. Specific ligand setups were proposed for selective separation of Co(II) and Ni(II) cations from each other. The materials were evaluated for recycling of rare earth based magnets, using simulation solutions corresponding to leachate from FeNdB and SmCo magnets.
9:55 AM
Recovery of Valuable Metals from End-of-life Lithium-ion Battery Using Electrodialysis: Ka Ho Chan1; Monu Malik1; Gisele Azimi1; 1University of Toronto
A novel electrochemical separation process was developed to recover lithium from an end-of-life lithium-ion battery of an electric vehicle using an environmentally friendly and cost-effective process based on electrodialysis. Lithium, nickel, manganese, and cobalt were first extracted from the cathode material of a spent lithium-ion battery through a hydrometallurgical leaching process using H2SO4+H2O2 leachant under the optimal operating conditions. After leaching, nickel, manganese, and cobalt were recovered as complex anions coupled with ethylenediaminetetraacetic acid chelating agent, whereas lithium was recovered as lithium hydroxide using electrodialysis. The results showed that almost 100% of lithium was separated from nickel, manganese, and cobalt. Future work is underway to improve and optimize the separation process.
10:15 AM
Lithium Adsorption Mechanism for Li2TiO3: Raja Shekhar Marthi1; York Smith1; 1University Of Utah
Layered H2TiO3 has shown promising selective lithium adsorption properties in lithium enriched brine solutions. However, the lithium adsorption mechanism of layered H2TiO3 is still not properly understood. It is currently accepted that lithium adsorption takes place via Li+-H+ ion exchange reaction without involving any breakage of chemical bonds. However, in this study we show that Li+- H+ ion exchange involves breaking of surface O-H bonds present in the HTi2 layers along with the formation of O-Li bonds. Using FTIR and Raman spectroscopy, we also show that the isolated surface hydroxyls are actively involved in lithium ion-exchange compared to hydrogen bonded surface hydroxyl groups, which are present in the interlayer spacings. This new proposed mechanism also explains the lower observed adsorption capacity from theoretical values.
10:35 AM
Study on the Production of Lithium by Aluminothermic Reduction Method: Huimin Lu1; Neale Neelameggham2; 1Beihang University; 2IND LLC
At present, the global production of 45,000 tons of lithium is obtained by molten salt electrolysis using lithium chloride as a raw material. Due to the release of chlorine gas in the production process, the environment is seriously polluted and the energy consumption is high. In this paper, lithium carbonate is used as a raw material, and aluminum powder is used as a reducing agent to extract metal lithium in a vacuum reduction furnace by aluminothermic reduction. The lithium recovery rate is 85% and the purity of metal lithium reaches 99.5%. In the laboratory, a continuous vacuum lithium reduction furnace was developed. No harmful gases were released during the entire production process. It was environmentally friendly.The production of lithium by aluminothermic reduction is a very promising method. The continuous lithium vacuum reduction furnace is the key equipment of this process, which lays the foundation for future industrial application.
10:55 AM Invited
Effect of Synthesis Method on the Electrochemical Performance of LiNixMnCo1-x-yO2 (NMC) Cathode for Li-ion Batteries: A Review: Monu Malik1; Ka Ho Chan1; Gisele Azimi1; 1University of Toronto
With high specific capacity and nominal voltage, low self-discharge, and low cost, layered LiNixMnCo1-x-yO2 (NMC) cathode has gained interest for second-generation lithium-ion batteries. Because the performance of lithium-ion batteries highly depends on the composition, crystallography, morphology, and other parameters during synthesis, interest in developing high-performance lithium-ion batteries has motivated researchers to develop novel synthesis methods to control these parameters. Although significant progress has been made in several synthesis methods such as sol-gel, hydrothermal, solid-state, emulsion, and wet chemical at lab scale, an industrially-viable synthesis approach is needed for cost-effective production of highly efficient NMC cathode materials. This paper summerise various synthesis methods investigated on lab and industrial scales for new and regenerated NMC cathode from end-of-life lithium-ion batteries and their effect on the battery performance. It is found that co-precipitation is the most commonly used method to produces NMC cathode, while spray pyrolysis is commonly used at the industrial scale.