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Générateurs photovoltaïques --- Solar batteries --- Générateurs photovoltaïques

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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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La quantité de déchets produits chaque année au sein de l’Union européenne augmente. Parmi ces déchets, le flux de déchets d’équipements électriques et électroniques (DEEE) connaît la croissance la plus prononcée. Les batteries lithium-ion font partie de cette classe de déchets. Ces batteries sont utilisées dans de nombreux appareils électroniques et sont également produites en grande quantité afin d’assurer la transition énergétique et écologique de la mobilité. Le recyclage de ces batteries est nécessaire afin de réduire leur impact écologique et de pouvoir réutiliser et sécuriser les matières premières critiques qui sont nécessaires à un certain nombre des technologies de la transition énergétique. Les différentes techniques de recyclage sont elles-mêmes sources de pollution et de nouvelles techniques de recyclage plus économiques et respectueuses de l’environnement sont en train d’émerger. La biolixiviation est une de ces techniques. Dans le cadre de ce travail, de la matière provenant de batteries lithium-ion a été fournie par un partenaire industriel. Après la caractérisation chimique et granulométrique de cette matière, différents tests de biolixiviation sont effectués afin d’étudier la possibilité de récupérer efficacement les métaux d’intérêt économique.

Biolixiviation --- Recyclage --- Batteries Lithium-ion --- Hydrométallurgie --- Ingénierie, informatique & technologie > Géologie, ingénierie du pétrole & des mines

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Notre production d’énergie repose actuellement principalement sur les ressources fossiles telles que le pétrole, le gaz et le charbon. Ces ressources sont polluantes et produisent énormément de gaz à effet de serre. Il est donc important de se tourner vers une transition énergétique mettant davantage l’accent sur l’utilisation d’énergies renouvelables et sur une meilleure efficacité énergétique. Les batteries peuvent avoir un impact très favorable, notamment grâce à leur couplage avec des panneaux photovoltaïques ou à de l’éolien. Cela permettrait, en effet, de mieux réguler l’énergie circulant sur le réseau et de mieux utiliser ces types d’énergies, qui sont intermittentes.
Ce travail a pour but de mieux comprendre ce qui concerne l’univers des batteries lithium-ion. Que ce soit au niveau de leur fonctionnement ou encore de l’impact de certains phénomènes sur leur comportement, tels que la température ou encore le vieillissement. Différentes méthodes d’utilisations de ces batteries ainsi que des techniques de modélisation de celles-ci sont décrites dans ce travail.
Afin de modéliser le comportement des batteries lithium-ion, les modèles inclus dans le logiciel TRNSYS ont été passés en revue et évalués. Ensuite, l’HTW Saar nous a proposé un modèle à circuit électrique équivalent qui pourrait correspondre à nos attentes. Enfin, un nouveau modèle de simulation de batteries lithium-ion a été développé dans Matlab, logiciel pouvant être couplé à TRNSYS. Le code proposé permet ainsi de modéliser l’évolution de l’état de charge de la batterie, la tension et l’intensité de celle-ci, ainsi qu’une puissance excédentaire et une puissance déficitaire. Le modèle prend également en compte le rendement du régulateur, celui de l’onduleur et pour terminer le rendement énergétique. The energy production of today is mostly based on fossil sources such as oil, gas and coal. These sources produce a lot of greenhouse gases. So, it is very important to aim towards an energy transition that use the renewable energies more effectively and that promote a better energy efficiency. The batteries can present a positive impact, mostly thanks to their combined use with photovoltaic panels or wind turbines. This could allow us a better management of the energy grid and a better use of those sporadic green energies.
This work aims a better understanding of the lithium-ion batteries. It can be about their operation or the impact of some phenomena on their behaviour, such as temperature or ageing. Various use methods and modelling techniques are described in this work.
With the target of modelling lithium-ion batteries, TRNSYS models have been evaluated. Then, an equivalent circuit model was suggested to us by the HTW Saar battery lab. Finally, a new model has been created using Matlab, linked to TRNSYS. The proposed code allows us to model the progress of the state of charge, the voltage, the current, an extra power and a lacking power. The model also considers the efficiency of the regulator and of the inverter. It also uses the energetic efficiency of the battery.

Batterie --- lithium-ion --- chimies de batteries --- vieillissement des batteries --- régulation du réseau --- simulation --- modèle --- TRNSYS --- Matlab --- battery --- lithium-ion --- battery chemistries --- battery ageing --- grid management --- simulation --- model --- TRNSYS --- Matlab --- Ingénierie, informatique & technologie > Energie

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Li-ion (LIB) batteries are a type of battery widely used in electric vehicles due to their specific characteristics. Their manufacture requires the use of critical raw materials such as cobalt, lithium, and nickel. Thus, the need to integrate the recycling of batteries at the end of their life is essential not only from an environmental point of view but also for the economic importance of these elements. 
The objective of the work is the study of anode and cathode separation technologies in a Li-ion battery in the upstream part of the process, by physical separation technologies, before entering the heat treatment. Two main technologies of mechanical separation were studied in this thesis including: A dry separation route by a pneumatic classifier with a vertical gas flow of the ZigZag type. The density separation tests handled in a lab and pilot scale proved that 34% of the total stream mass could be discarded in losing only 8% of the cathode.
Electrostatic separation is another potential technique that uses the conductivity properties of the battery components to achieve a good separation between anode and cathode, by concentrating anodes in the conductive bin. It allows to recover up to 75% of copper in the conductive fraction for a total yield of 36% and an anode grade of 17% with only 4% cathode loss.

Li-ion batteries recycling --- blackmass --- gravity separation --- electrostatic separation --- DryCells --- Image processing --- Python --- Ingénierie, informatique & technologie > Science des matériaux & ingénierie