Lithium-ion batteries play an important role in our modern society as the main option to power portable electronic devices and electric vehicles. The growing demand for these batteries encourages the development of more efficient recycling processes, aiming to decrease the environmental impact of the spent batteries and recover their valuable components. In this paper, a combined hydrometallurgical-electrodialytic method is proposed for processing battery waste. In the combined technique, the amount of leaching solution is reduced as acid is generated via electrolysis. At the same time, the use of ion-exchange membranes and the possibility of electroplating allows for a selective separation of the target metals. Experiments were performed using LiCoO2, which is one of the most used cathodes in lithium-ion batteries. First, 0.1 M HCl solution was used in batch extractions to study the kinetics of LiCoO2 dissolution, reaching an extraction of 30% and 69% of cobalt and lithium, respectively. Secondly, hydrometallurgical extraction experiments were carried out in three-compartment electrodialytic cells, enhanced with cation-exchange membranes. Experiments yielded to a selective recovery in the catholyte of 62% of lithium and 33% of cobalt, 80% of the latter electrodeposited at the cathode.
The use of lithium-ion batteries as energy storage in portable electronics and electric vehicles is increasing rapidly, which involves the consequent increase of battery waste. Hence, the development of reusing and recycling techniques is important to minimize the environmental impact of these residues and favor the circular economy goal. This paper presents experimental and modeling results for the hydrometallurgical treatment for recycling LiCoO2 cathodes from lithium-ion batteries. Previous experimental results for hydrometallurgical extraction showed that acidic leaching of LiCoO2 particles produced a non-stoichiometric extraction of lithium and cobalt. Furthermore, the maximum lithium extraction obtained experimentally seemed to be limited, reaching values of approximately 65–70%. In this paper, a physicochemical model is presented aiming to increase the understanding of the leaching process and the aforementioned limitations. The model describes the heterogeneous solid–liquid extraction mechanism and kinetics of LiCoO2 particles under a weakly reducing environment. The model presented here sets the basis for a more general theoretical framework that would describe the process under different acidic and reducing conditions. The model is validated with two sets of experiments at different conditions of acid concentration (0.1 and 2.5 M HCl) and solid to liquid ratio (5 and 50 g L−1). The COMSOL Multiphysics program was used to adjust the parameters in the kinetic model with the experimental results.
Zero valent iron (ZVI) is being used in permeable reactive barriers (PRB) for the removal of oxidant contaminants, from nitrate to chlorinated organics. A sound design of these barriers requires a good understanding of kinetics. Here we present a study of the kinetics of nitrate reduction under relatively low values of pH, from 2 to 4.5. We use a particle size of 0.42 mm, which is within the recommended size for PRBs (0.2 mm to 2.0 mm). In order to avoid possible mass-transfer limitations, a well-stirred reactor coupled with a fluidized bed reactor was used. The experiments were performed at constant pH values using a pH controller that allows to accurately track the amount of acid added. Since the reduction of H + to H 2 by the oxidation of ZVI will always be present for these pH values, blank experiments (without nitrate) were performed and the rate of this H + reduction obtained. This rate of reduction was studied using three kinetic models: a regular empirical one, the Shrinking-Core Model (SCM), and the Surface Kinetics Model (SKM). The best performance was obtained from the SKM model. Therefore, this model was also used to study the results for the nitrate reduction, also with satisfactory results. In both cases, some assumptions are introduced to maintain a moderate number of fitting parameters.
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