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Color centers --- Lithium compounds --- Centres colorés. --- Lithium --- Composés.

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The aim of the present master's thesis is to develop and optimize a method to recover lithium in the filtrate of a lithium primary batteries recycling process. The importance of recycling lithium primary batteries lays in the fact that there is currently no process used at an industrial scale able to treat that kind of cells because of the practical and safety issues related to their nature. 

In this context and despite their small market share, Revatech decided to work on that type of batteries as they cannot be safely stored and need to be treated to minimize risks of explosion due to their high reactivity. The treatment of these cells generates three fractions: scrap metal, black-mass and a liquid concentrate of lithium. This document focuses on the liquid output.

The first step of the thesis is the documentation on already implemented batteries recycling and lithium recovery processes which can give a hint on the available methods. Since information on lithium-ions batteries are more available, the methods described in scientific literature often have to be adapted to the case of lithium primary batteries.

The recovery of lithium in this filtrate is done by selective precipitation using sodium carbonate to recover solid lithium carbonate.

The adjustment of parameters and the experiments on different types of filtrate are done to come to a recovery rate and purity as high as possible on a representative filtrate generated by the shredding of a mix of different types of lithium primary batteries. After optimization, a recovery rate of 80% and a purity of 99% are reached.

The parameters eventually used are a molar ratio Na/Li of 1.5, a volume of water to wash the precipitate equals to 50% of the volume of the initial lithium containing solution, a reaction time of 30 minutes and working at room temperature.

These parameters are initially tested on lithium hydroxide solution allowing experiments on pollutant free solutions containing only lithium before their application to a filtrate generated by the shredding of batteries.

The results are extrapolated to forecast the production possibilities related to this process. The experiments led to a potential volume of 110 m³ of filtrate to process in order to produce 7tons of lithium carbonate taking 300 tons of batteries (Revatech forecast) as an input. Further intermediate tests still have to be made but if a scale-up with the same output as the lab experiments is reached, it would be profitable for the company and could be done without transforming the current plant.

Lithium recovery --- Lithium primary batteries --- lithium recycling --- Physique, chimie, mathématiques & sciences de la terre > Chimie

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Ces dernières décennies, les applications de batteries de type lithium-ion se sont accrues exponentiellement et particulièrement dans le domaine des nouvelles technologies. Parmi celles-ci, la catégorie de batteries la plus retrouvée sur le marché présente une cathode de type Nickel-Manganèse-Cobalt (NMC), dont la proportion en cobalt a diminué au profit de manganèse et de nickel. De ce fait, les méthodes dites de pyrométallurgie deviennent moins rentables. Les nouveaux acteurs du recyclage des batteries se tournent dès lors vers les procédés hydrométallurgiques plus flexibles d’une part et qui permettent la récupération efficace de plusieurs métaux d’autre part. 
L’objectif de ce travail est de proposer un procédé alternatif de type hydrométallurgique basé sur l’extraction par solvant afin de récupérer tous les éléments constitutifs de la cathode. Nous avons étudié l’intérêt de la mise en place d’une unité de coextraction de cobalt et de manganèse par le Cyanex 272 (extractant). Le but est de produire d’une part un concentré de Co-Mn séparable aisément par la suite et d’autre part un raffinat enrichi en nickel. Ces deux produits peuvent être par la suite valorisés en sulfate de cobalt, nickel et manganèse, tous des précurseurs de matériel cathodique. Les données expérimentales ont permis de construire les diagrammes de McCabe-Thiele qui permettent de déterminer les paramètres de conception de l’unité de traitement. L’extraction se fait en quatre étapes (avec un rapport O/A de 4) et le strippage en une étape avec un rapport O/A égal à trois. On remarque cependant qu’une telle installation sera difficilement rentable actuellement, à cause principalement des coûts liés aux importants volumes de phase organique estimés.

Recycling --- Lithium-ion batteries --- Hydrometallurgy --- Solvent extraction --- Ingénierie, informatique & technologie > Géologie, ingénierie du pétrole & des mines

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Kidney --- Lithium --- Kidney Tubules --- Potassium --- drug effects --- adverse effects --- drug effects --- pharmacology

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Due to its high consumption and unequal distribution of primary lithium resources such as minerals and brines, lithium, a key component in LIBs, is experiencing an economic and supply crisis. Thus, it has been added to the EU critical raw material list since 2020. And a target of 50% lithium recycling from LIBs is set by the end of 2027 in Directive 2006/66/EC. This research aims to develop an economical and environmentally friendly process for recycling lithium from the leachate after LIB recycling. It will benefit in meeting the EU lithium recycling target, industrial growth, sustainability in the lithium value chain, the circular economy, and industrial wastewater regulations.
In the methodology, crystallization experiments were carried out by cooling the Li solution at 1 °C for 20 to 48 hours to remove Na impurities. Moreover, chemical precipitation experiments were 
conducted to precipitate Li2CO3. The pH of the solution was adjusted with NaOH and heated to the desired temperature, followed by the saturated sodium carbonate addition. The reaction time was 60 minutes to reach equilibrium. The slurry was filtered, and the wet precipitates were heated at 100 °C for 1 hour. Moreover, the same methodology was applied to the solution with chloride chemistry after ion exchange resin.
From the results, crystallization removed 49.67% Na from the Li solution in 20 hours. In chemical 
precipitation, temperature, pH value, Li concentration, and CO3/Li+ ratio are observed to be 
influential parameters on recovery and grade. The Li recovery of 80.91% with 96.40% Li2CO3 purity was obtained at 95 °C, CO3/Li+ 1.075, and 10.45 g/L Li concentration after crystallization. The purity can be improved to 99.56% by repulping precipitates with hot water with minimal loss of Li recovery and less than 0.42% Na content. On the other hand, the solution after ion exchange resin obtained 80.44% recovery at 70 °C, CO3/Li+ 1.0, and 8.32 g/L Li with 99.40% purity without repulping and 0.26% Na. Thus, the solution with less Na impurity and chloride chemistry needs less temperature to precipitate lithium carbonate.
Nevertheless, during the economic analysis, the ion exchange resin phase appeared costly. As the elution step gives lithium concentration of 0.9 g/L, it requires a substantial amount of energy to concentrate lithium. Conversely, the experimental outcomes after the crystallization phase revealed cost-effectiveness and fewer energy requirements across the entire process. Consequently, an economically viable flowsheet for the targeted recovery of lithium as lithium carbonate from the leaching solution after the LIB recycling is formulated and presents a potential industrial proposition.

Lithium-Ion Batteries --- Recycling --- Hydrometallurgy --- Chemical Precipitation --- Crystallization --- Ion Exchange Resin --- Lithium Carbonate --- Sodium Carbonate --- Economic Analysis and Scale-Up --- Ingénierie, informatique & technologie > Géologie, ingénierie du pétrole & des mines