Made available in DSpace on 2018-08-01T21:58:45Z (GMT). No. of bitstreams: 1 tese_10233_Thamyres Fernandes Messa Moreira20170116-145305.pdf: 3284740 bytes, checksum: ab4ac23a7af942990086e3906900baec (MD5) Previous issue date: 2016-08-18 / A reciclagem de baterias Ni-Cd exauridas é importante por razões ambientais, cientificas e econômicas podendo ser realizada, principalmente, por processos pirometalurgicos e hidrometalurgicos. Neste trabalho, foram desenvolvidas rotas hidrometalurgicas para a reciclagem dos eletrodos positivos e negativos de baterias Ni-Cd. O eletrodo negativo foi lixiviado com ácido sulfúrico (H2SO4) 0,50 mol L-1 e o eletrodo positivo em ácido cítrico (C6H8O7) 0,50 mol L-1 . O objetivo do trabalho foi a síntese e caracterização de filmes de cádmio metálico, óxido de cádmio e óxido de níquel, cádmio, cobalto e ferro. Os óxidos foram aplicados em processos de fotocatalíticos. Os filmes de cádmio metálico foram formados com auxilio da técnica galvanostática sob as condições: densidade de corrente de -28 mA cm-² e densidade de carga variando em 11,4 C cm-2 e 28,4 C cm-2, densidade de corrente de -56 mA cm-2 e densidade de carga de 11,4 C cm-2 e 28,4 C cm-2. A eficiência máxima de deposição de cádmio alcançou 84,87% e a reação de evolução de hidrogênio no sistema ocorre simultaneamente a redução do cádmio. Realizou-se a síntese do óxido de cádmio (CdO) a partir do tratamento térmico do precursor de carbonato de cádmio (CdCO3). O CdO obtido tem tamanho médio de cristalito de 22,21 nm e foi caracterizado por espectroscopia de Infravermelho (IV-TF), difração de raios X (DRX) e microscopia eletrônica de transmissão (MET). O óxido metálico sintetizado por método sol-gel apresentou composição mista contendo óxido de níquel (NiO), CdO, óxido de cobalto (Co3O4) e óxido de Ferro (Fe2O3) sendo denominado de NiO/CdO/Co3O4/Fe2O3 e caracterizado por IV-TF, DRX, MEV, espectroscopia de raios X por dispersão em energia (EDX), microscopia eletrônica de transmissão (MET) e espectrometria de emissão ótica com plasma indutivamente acoplado (ICP OES). Os óxidos sintetizados foram aplicados no processo de degradação do corante têxtil Preto Reativo V-2B. Os óxidos CdO e NiO/CdO/Co3O4/Fe2O3 apresentaram comportamento catalítico e a eficiência de degradação não depende do pH. A maior eficiência de degradação do corante obtida para o CdO foi de 67,10% e para o NiO/CdO/Co3O4/Fe2O3 de 86,30% após 480 minutos de análise

Diploma thesis is involved in basic properties of nickel materials for alkaline accumulators. Practical part deals with measuring of nickel hydroxides by cyclic voltametry. Next practical part is above measuring and optimalization various proportion of nickel and cobalt in layer made by electrodeposition on nickel electrodes.

This thesis is involved in basical properties of electrode materials for alkaline accumulators. This thesis describes the possibilities of capacity stabilisation of nickel electrode to be stable for highest number of cycles. Thesis also consider modification of properties of electrode materials on the base of nickel hydroxide by using dopes (aluminum, manganese). Measuration proceeded on the thin film electrodes created by electrodeposition. Measuration of properties of electrodes proceeded by cyclic voltammetry and frequency analyzis.

This master's thesis is concerned with the influence of aluminate ions added in various concentrations into the structure of nicel hydroxide that creates Ni-Cd accumulators positive electrode active mass basis nowadays. Nicel hydroxide occurs in two basic modifications ? and ß. Nowadays used ß modification reaches low capacity in comparison with ? modification. The disadvantage of ? modification is its instability and gradual degradation to ß modification. The aim of this diploma paper is to select the optimal amount of aluminate additives into the structure of nicel hydroxide with regard to electrochemical efficiency, stability, and degradation degree of the accumulated layer.

The Master´s thesis deals with description of the influence of cobalt additive on positive electrode parameters for Ni-Cd accumulators. Trough the use of Electrochemical Quartz Crystal Microbalance are analysed the effects which decline effective life of positive electrode during accelerated cycling. Theoretical part describes important characteristics of Ni-Cd accumulators, the working principle and effects which are in progress on positive electrode during cycling. The next part deals with description of system EQCM and the pricnciples of doping active mass with cobalt additive. Practical part consists of EQCM system calibration and electrochemical measurements. The principal aim is detection of the influence of cobalt additve on active mass during cycling in different electrolytes. From the results of measurements is set the optimal amount of cobalt additive.

La tesis realizada se engloba dentro de los sistemas de carga rápida de baterías de media y gran capacidad. Dentro de esta tesis se ha desarrollado una metodología de ensayos original para el estudio de los procesos de carga de baterías de Ni-Cd y de Ni-MH. Además se ha propuesto un método de finalización de carga rápida original. El contenido de la tesis es el que se describe a continuación:En el capítulo 1 se estudia el estado del arte relacionado con las distintas tecnologías de baterías utilizadas en sistemas que funcionan bajo regímenes cíclicos de carga-descarga (plomo-ácido, níquel-cadmio, níquel-hidruro metálico y litio-ión). Además, se seleccionan las tecnologías más adecuadas para el funcionamiento en regímenes cíclicos de carga-descarga (Ni-Cd y Ni-MH), se plantea la problemática de la carga rápida y se establecen los objetivos del trabajo.En el capítulo 2 se realiza el estudio de las características de descarga de las tecnologías de baterías seleccionadas (Ni-Cd y Ni-MH).En el capítulo 3 se presenta una metodología de ensayos original desarrollada específicamente para el estudio de los procesos de carga en baterías de Ni-Cd y Ni-MH de media y gran capacidad (carga lenta y carga rápida). Además, se presentan los bancos de ensayos desarrollados para la realización de los ensayos de carga.En el capítulo 4 se realiza un exhaustivo análisis de los procesos de carga en baterías de Ni-Cd y Ni-MH basándose en diferentes índices de comportamiento como son: evolución de la tensión y de la temperatura, capacidad cargada y descargada, aceptación de carga, eficiencia energética, etc. Este estudio aporta una valiosa información dada la novedad de las baterías en estudio.En el capítulo 5 se realiza un análisis crítico de los métodos de carga actuales desde el punto de vista de su posible aplicación en carga rápida en baterías de media y gran capacidad.En el capítulo 6 se propone un método original de finalización de carga que junto a la selección de la razón de carga óptima en cada tecnología dan lugar a un método de carga preciso, fiable, fácil de implementar y económico.En el capítulo 7 se resumen las principales conclusiones y aportaciones de la tesis y las líneas futuras de trabajo.

Ce mémoire porte sur le développement d'un protocole d'extraction sélective de métaux présents dans les accumulateurs Ni-Cd en fin de vie. Classiquement, les procédés hydrométallurgiques appliqués à ce type de solides comportent de nombreuses étapes dont les principales sont la lixiviation et la récupération du métal par électrolyse. Le procédé utilisé permet le couplage des opérations d'Electrolixiviation et d'Electrodéposition (noté E/E) au sein d'une même cellule. La technique est basée sur la lixiviation de la matière active des accumulateurs Ni-Cd par les protons générés à l'anode, les cations lixiviés (Co2+, Ni2+ et Cd2+) migrent vers la cathode où le cadmium est sélectivement réduit. Nous avons étudié les possibilités de récupération des métaux, mais également tenté d'appréhender les phénomènes prenant place dans la cellule lors du couplage E/E. Dans un premier temps, nous avons choisi de démanteler manuellement des accumulateurs en raison de la complexité des broyats industriels. La matière active des accumulateurs Ni-Cd a été caractérisée. Sa composition moyenne est la suivante :Cd(OH)2 : 45,3 %, Cd0 : 0,02 %, Ni(OH)2 : 30,0 %, Ni0 :12,9 %, NiOOH : 0,9%, Co(OH)2 : 2,4 %. Au vu des différentes formes minéralogiques présentes, ce solide peut être considéré comme un déchet modèle pour ce traitement. Avant d'envisager le couplage E/E, la lixiviation chimique de la matière active par H2SO4 a d'abord été étudiée. La modélisation de cette opération a mis en évidence que la cinétique de dissolution de Cd(OH)2 est gouvernée par le transfert de masse des protons, la dissolution de Ni(OH)2 et Co(OH)2 étant quant à elle régie par la réaction chimique de surface. Dans ces conditions de lixiviation douce, le nickel métallique n'est pas oxydé et se retrouve dans le résidu solide avec le carbone. Nous avons pu démontrer ensuite la sélectivité de l'électrodéposition vis-à-vis du Co2+ et du Ni2+ avec un rendement faradique d'environ 99 % à une densité de courant de 350 A.m-2. L'étude cinétique de l'E/E a montré que l'électrolixiviation est l'étape limitante du procédé, phénomène qui a également été modélisé. L'E/E appliquée aux matériaux d'électrodes permet en 5 h 30 de lixivier 97 % du cadmium initialement présent. Le solide résiduel est composé à 82 % de nickel, principalement sous la forme métallique, 4 % de cadmium, 0,5 % de cobalt et 3 % de carbone. Le dépôt de cadmium est obtenu avec une pureté supérieure à 97 % et un rendement faradique de déposition supérieur à 74 % à une densité de courant de 350 A.m-2. La faisabilité du couplage E/E appliqué au traitement d'accumulateurs Ni-Cd en fin de vie a été démontrée malgré la complexité de la matrice. Les premiers essais d'application de ce traitement à des échantillons industriels (Cd(OH)2 : 36,1 %, Ni(OH)2 : 24,1 %, Ni0 : 16,6 %, NiOOH : 5,5 %, Co(OH)2 : 2,4 % et Fe :1% en masse) confirment les résultats obtenus avec les matériaux d'électrodes provenant du démantèlement manuel / This thesis focuses on the development of a protocol for selective extraction of metals from spent Ni-Cd batteries. Conventionally, hydrometallurgical processes applied to this type of solids involve several steps, the main ones being the leaching and the metal recovery by electrolysis. The method used consists in coupling Electroleaching to Electrodeposition operation (denoted E/E) within the same cell. The technique is based on the leaching of the active material of Ni-Cd batteries by protons generated at the anode: the cations (Co2+, Ni2+ and Cd2+) released by leaching migrate to the cathode where the cadmium is selectively reduced. We studied the possibility of metals recovery, but also tried to understand the phenomena occurring in the cell during the E/E experiments. Initially, it was preferred to manually dismantle batteries due to the complexity of industrial waste crushed. The active matter of Ni-Cd has been characterized. Its average composition is as follows: Cd(OH)2: 45.3%, Cd0: 0.02%, Ni(OH)2: 30.0%, Ni0: 12.9%, NiOOH: 0.9%, Co(OH)2: 2.4%. In view of these different mineralogical forms, this solid can be considered a model for the waste treatment. Before considering the E/E treatment, chemical leaching of the active matter by H2SO4 was first studied. Modelling of the tests carried out showed that the kinetics of Cd(OH)2 dissolution is governed by mass transfer of protons and the dissolution of Ni(OH)2 and Co(OH)2 by the surface chemical reaction. Under these conditions of soft leaching, metal nickel is not oxidized and is found in the solid residue, with carbon. We had to demonstrate the cadmium electrowinning selectivity, for separation from Co2+ and Ni2+ species, with a current efficiency up to 99% at a current density of 350 A.m-2. The kinetic study of the E/E showed that electroleaching is mainly governed by H+ generation at the anode. Besides, the overall process is largerly controlled by cations transport from the anode to the cathode side: this transport phenomenon had also been modeled. The E/E applied to the electrode materials for 5 h 30 allows the leaching of 97% of the cadmium initially present. The residual solid is composed by 82% of nickel, mainly in the metallic form, 4% of cadmium, 0.5% of cobalt and 3% carbon. The deposition of cadmium is obtained with a purity greater than 97% and a current efficiency greater than 74% at a current density of 350 A.m-2. The feasibility of the E/E coupling applied to the spent Ni-Cd batteries treatment has been demonstrated despite the complexity of the matrix. The first tests to apply this treatment to industrial samples (Cd(OH)2: 36.1% Ni(OH)2: 24.1% Ni0: 16.6% NiOOH: 5.5% Co(OH)2: 2.4% and Fe: 1% by weight) confirm the results obtained with the electrode material from the manual dismantling

This dissertation work deals with analysis of nickel hydroxide phases, their oxidation compounds, their stability and degradation mechanisms of electrochemically more active alpha phase on standard beta phase. The active material was prepared by both methods, electrodeposition and chemical precipitation. Main analysis method was Electrochemical Quartz Crystal Microbalance in combination with common analytical methods (cyclic voltammetry, potenciometry) can resolute between alpha and beta phases and quantitatively describe differences in main reaction by monitoring mass changes in the active material. Poor stability of the ?-Ni(OH)2 were improved by adding cations with valence two three and four into the structure instead of Ni atoms. The most important role plays cobalt and its hydroxide. Totally new way is to use titanium in combination with other cations. In electrolyte the most significant addition is LiOH, which has beneficial influent on cycle ability, stability in strong alkaline medium and cycle life.

The aim of my diploma thesis was to explore the influence of manganese ions put into nickel nitrate structure. The attention was focused mainly on the stabilization of nickel nitrate a modification, which could not change into b modification. The theoretical part of my thesis focused on applied materials, kinds of acumulators, basic parameters of acumulators and the description of chosen methods of measurement employed. It contained the electrodeposition, the impedance spectroscopy and the cyclic voltammetry. The task of the experimental part was to measure the effect of manganese ions put into potassium hydroxide structure. Proportions of Ni (nickel nitrate) : Mn (manganese nitrate) 10:0, 7:3, 5:5, 6:1 and 6:4 were blended for the measurement. By means of the electrodeposition, there was a thin layer of nickel hydroxide with an admixture of manganese ions from nickel nitrate and manganese nitrate dilution put on the nickel plate. After the spread of the thin layer on the nickel plate, the measurement by the method of cyclic voltammetry followed. The next task consisted in trying to add KOH (potassium hydroxide) anionic and cationic surfactant into the dilution.