Made available in DSpace on 2018-08-01T21:58:49Z (GMT). No. of bitstreams: 1 tese_12206_Luma Barbosa Magnago.pdf: 1956140 bytes, checksum: 16d722634803eabf0f76fd98302d22f7 (MD5) Previous issue date: 2018-03-16 / Neste trabalho, o método de co-precipitação foi utilizado para a síntese de ferritas não dopadas (Fe2O3/Fe3O4-R) e dopadas com níquel a partir de reagentes comerciais (NiFe2O4-R) e a partir do níquel reciclado de baterias de níquel hidreto-metálico (Ni-MH) exauridas (NiFe2O4-B). A estrutura e composição das ferritas foi confirmada por difratometria de raios X (DRX), espectroscopia dispersiva de raios X (EDX) e espectrometria com plasma indutivamente acoplado (ICP OES). A microscopia eletrônica de varredura (MEV) mostrou que as ferritas são formadas por partículas aglomeradas de diferentes tamanhos e formatos e a microscopia eletrônica de transmissão (MET) revelou partículas esféricas de 50 nm, aproximadamente. Ferritas são materiais multifuncionais que podem ser utilizados como catalisadores e pseudocapacitores. A propriedade catalítica das ferritas foi analisada através da descoloração do corante azul de metileno (AM) pelo processo foto Fenton heterogêneo utilizando radiação solar. O planejamento experimental apontou as ferritas na seguinte ordem referente a eficiência de descoloração do corante: NiFe2O4-B = NiFe2O4-R > Fe2O3/Fe3O4-R. Utilizando a NiFe2O4-B, a solução do AM foi descolorida com mais de 90% de eficiência em 90 minutos. A análise por ICP OES da solução final após descoloração com a NiFe2O4-B indicou uma concentração de (0,00057 ± 0,00067) 𝑚𝑔L-1 de íons de níquel e não detectou-se íons de ferro. As concentrações de íons de níquel e de ferro estão abaixo do recomendado pela resolução 430/2011 do CONAMA para o descarte de efluentes. NiFe2O4-B não transfere íons metálicos presentes em sua composição para a solução. Na solução final também foram identificados os ácidos fórmico, acético e propiônico por cromatografia de íons (CI). A propriedade pseudocapacitiva das ferritas foi analisada por voltametria cíclica (VC) e mostrou que a NiFe2O4-B possui maior eficiência de carga (84,3%) quando comparada com as ferritas NiFe2O4-R (65,5%) e Fe2O3/Fe3O4-R (57%) após 1000 ciclos. A ferrita NiFe2O4-B é um eficiente catalisador na degradação do corante AM e ainda pode ser utilizado como um pseudocapacitor eletroquímico.

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Made available in DSpace on 2016-12-23T14:41:49Z (GMT). No. of bitstreams: 1 Vinicius Emmanuel de Oliveira.pdf: 5229003 bytes, checksum: 7bc46aad5447805d1e99c00c4deb6f3b (MD5) Previous issue date: 2012-08-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, um método hidrometalúrgico para a recuperação dos metais terras raras, cobalto, níquel, ferro e manganês dos eletrodos negativos exauridos das baterias de telefone celular é desenvolvido. Os compostos das terras raras foram obtidos por precipitação química em pH 1,5 com NaCe(SO4)2.H2O e La2(SO4)3.H2O como os principais componentes recuperados. A composição e a concentração relativa dos elementos químicos que constituem os materiais recuperados foram determinados por espectroscopia de emissão óptica com plasma indutivamente acoplado (ICP-OES).Esta análise confirma que os elementos níquel, cobalto,ferro e manganês permanecem em solução após a precipitação do cério e lantânio. O ferro é recuperado como Fe(OH)3 e FeO. Além disso o precipitado de hidróxido de manganês inicialmente formado sofre um processo de envelhecimento em soluções alcalinas e na presença de oxigénio, manganês é obtido como Mn3O4. Níquel e cobalto foram recuperados como β -Ni(OH)2 e Co(OH)2. Os hidróxidos recuperados de cobalto e níquel são subsequentemente utilizados para sintetizar materiais de cátodos LiCoO2,LiNiO2 e CoO para uso em baterias de Li-ion. Os ânodos e materiais reciclados são caracterizados por difração de raios - X (DRX), microscopia eletrônica de varredura (MEV), energia dispersiva de raios-X, (EDX), espectroscopia de infravermelho com transformada de fourier (FT-IR), termogravimetria (TG/DTG) e espectroscopia de emissão óptica com plasma indutivamente acoplado (ICP-OES). Métodos químicos e eletroquímicos para reciclagem de Ni, Co, Zn e Mn dos eletrodos positivos exauridos de baterias de Ni-MH foram desenvolvidos. Os materiais reciclados por precipitação química tem a composição β - Ni(OH)2, Co(OH)2, Zn(OH)2 e Mn3O4. O pó retém, nitrato,sulfato e carbonato de ânios a partir da solução mãe, bem como água adsorvida.Estudos utilizando voltametria cíclica mostram que a densidade de corrente diminui para taxas de varredura maiores que 10 mVs-1 por causa da formação de filmes de hidróxido. As quantidades de Ni2+,Co2+,Zn2+ e Mn2+ foram obtidas por análise da solução utilizando espectroscopia de emissão óptica com plasma indutivamente acoplado (ICP-OES), que demonstraram que o método de eletrodeposição exibe um comportamento anómalo. As quantidades de íons de níquel depositado está relacionado com a composição dos banho de sulfamato. A presença de manganês nos eletrodepósitos é devido à precipitação do Mn(OH)2 e Zn(OH)42- não sofre redução no intervalo investigado de potencial. O material eletrodepositado contém Ni, Co, CoO, Co(OH)2, e Mn3O4. Uma eficiência da carga de 83,7 % foi obtida para os eletrodepósitos formados por aplicação de -1,1 V vs Ag /AgCl a uma densidade de corrente de - 90 Ccm-2. A dissolução dos eletrodepósitos depende do potencial aplicado / In this work, a hydrometallurgical method for the recovery of rare earth metals, cobalt, nickel, iron, and manganese from the negative electrodes of spent Ni-MH mobile phone batteries is developed. The rare earth compounds are obtained by chemical precipitation at pH 1.5 with NaCe(SO4)2.H2O and La2(SO4)3.H2O as the major recovered components. The composition and relative concentration of the chemical elements that constitute the recovered material are determined by inductively coupled plasma optical emission Spectroscopy (ICP-OES). This analysis confirms that the elements cobalt, nickel, iron, and manganese remain in solution after precipitation of the cerium and lanthanum. Iron is recovered as Fe(OH)3 and FeO. In addition, because manganese hydroxide precipitate initially undergoes an aging process in alkaline solutions and in the presence of oxygen, manganese is obtained as Mn3O4. Nickel and cobalt are recovered as β-Ni(OH)2 and Co(OH)2. The recovered cobalt and nickel hydroxides are subsequently used to synthesize the cathode materials LiCoO2, LiNiO2 and CoO for use in Li-ion batteries. The anodes and recycled materials are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), fourier transform infrared spectroscopy (FT-IR), thermogravimetry (TG/DTG) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Chemical and electrochemical recycling methods for the Ni, Co, Zn and Mn from the positives electrodes of spent Ni-MH batteries were developed. The materials recycled by chemical precipitation has the composition β-Ni(OH)2, Co(OH)2, Zn(OH)2 and Mn3O4. The powder retains, sulphate, nitrate and carbonate anions from the mother solution as well as adsorbed water. Studies using cyclic voltammetry show that the current density decreases for scan rates greater than 10 mV s-1 because of the formation of hydroxide films. The amounts of Ni2+, Co2+, Zn2+ and Mn2+ were obtained by analysis of the solution using the inductively coupled plasma with optical emission spectroscopy technique, which demonstrated that the electrodeposition method exhibits anomalous behavior. The amount of deposited nickel ions is related to the composition of the sulfamate bath. The presence of manganese in the electrodeposits is due to the precipitation of Mn(OH)2, and Zn(OH)42- does not undergo reduction in the investigated potential range. The electrodeposited material contains Ni, Co, CoO, Co(OH)2, and Mn3O4. A charge efficiency of 83.7% was attained for the electrodeposits formed by the application of -1.1 V vs. Ag/AgCl at a current density of -90 C cm-2. The dissolution of the electrodeposits depends on the applied potential

Une alternative aux énergies fossiles comme vecteur énergétique peut se présenter sous la forme de l'hydrogène et de son stockage. Les hydrures métalliques sont une des options possibles pour le stockage de l'hydrogène. Les accumulateurs alcalins Ni-MH présentent une technologie intéressante pour les applications portables et pour le développement des véhicules électriques hybrides (HEV). Afin de répondre à la demande d'augmentation de la capacité massique des accumulateurs, de nouveaux composés intermétalliques hydrurables de type ABx (3etlt;xetlt;5) sont étudiés. Le groupe A est constitué de terres rares partiellement substituées par du magnésium, le groupe B contient du Ni. Après un état de l'art sur ce type de composés, le travail de cette thèse consiste à rechercher les conditions d'élaboration des composés A1-yMgyNix (3etlt;xetlt;5, 0etlt;yetlt;1, A= La, Pr, Nd) ainsi que de les caractériser d'un point de vue structural et physico-chimique (DRX, microsonde électronique, ICP) et de déterminer leurs propriétés vis-à-vis de l'hydrogène (réac tion solide-gaz et électrochimique). Durant ce travail de nouvelles phases ont été découvertes et caractérisées : les phases (A1-yMgy)5Ni19 / One solution to overcome the diminution of fossil fuel resources is to use hydrogen as an energy vector. The main issue concerning hydrogen systems is its storage. NiMH batteries are promising candidates for portable devices and hybrid vehicles (HEV) applications. In order to answer to growing need for higher capacity, new compounds such as ABx (3etlt;xetlt;5) are under investigation. A is a rare earth element that can be partially substituted by Mg. B is Ni. After careful examination of the state of the art on this family of compound, the synthesis routes to prepare A1-yMgyNix (3etlt;xetlt;5, 0etlt;yetlt;1, A= La, Pr, Nd) alloys were investigated and optimized during this PhD work. The structure and chemical composition of the samples were determined using X-ray diffraction, microprobe analysis and ICP. The hydrogen sorption properties (solid-gas and electrochemical reactions) were studied as well. During this work the (A1-yMgy)5Ni19 new phase s have been reported and characterized

Les applications portables et stationnaires des accumulateurs Ni-MH nécessitent sans cesse des autonomies de plus en plus importantes. Cet accroissement d’autonomie peut être obtenu en développant de nouveaux composés intermétalliques hydrurables de type ABx (3<x<4) de plus grande capacité massique. Le groupe A de ces composés est constitué de La partiellement substitué par du Mg, qui est beaucoup plus léger et diminue la masse molaire de l’alliage, et le groupe B contenant du Ni partiellement substitué par d’autres éléments de transition. Après une étude bibliographique approfondie, le travail de cette thèse consiste à rechercher tout d’abord les conditions optimales d’élaboration d’intermétalliques de composition La1-yMgyNix (0<y<1 ; 3<x<4). Puis ces composés sont caractérisés du point de vue structural et physico chimique (diffraction des rayons X et microsonde électronique), et leurs propriétés vis-à-vis de l’hydrogène (réaction solide-gaz et électrochimique) sont étudiées / Mobile and stationary applications for Ni-MH batteries require continuously more and more energy density. This increased autonomy can be obtained by developing new hydride-forming compounds of ABx-type (3<x<4) with larger weight capacities. The A element of these compounds is constituted of La partially substituted by light Mg, allowing a reduced molar weight. The B element is made of Ni that can be partially substituted by other transition metals. After an extensive bibliographic study, this thesis presents the research work to find optimum conditions for the synthesis of Mg-containing intermetallic compounds La1-yMgyNix (0<y<1; 3<x<4). These compounds are then characterized from the structural and chemical point of views (X-ray diffraction and microprobe analysis) and their hydrogen-related properties are studied and compared (solid-gas and electrochemical reactions)

Cette thèse vise à améliorer les propriétés d'alliage à mémoire de forme et de stockage d'hydrogène du TiNi par des substitutions chimiques sur le sous-réseau de Ni. L'effet de la substitution de Ni par Pd, Cu et Co sur les propriétés structurales, la transformation martensitique et les propriétés d'hydrogénation de TiNi, a été étudiée par des techniques structurales (diffraction des Rayons-X et des neutrons sur poudre), calorimétriques, par réaction solide-gaz et par mesure électrochimique. Des calculs de type DFT ont été effectués pour mettre en évidence les modifications de la structure électronique sur les propriétés d'hydrogénation. Les trois substitutions, TiNi1-zMz (M = Pd, Cu et Co; z ≤ 0,5), conduisent à la formation de composés pseudo-binaires. La substitution par Pd et par Cu augmentent le volume de la maille de TiNi, alors que celle par Co possède un effet inverse. Les températures de transformation martensitique suivent la même tendance que les changements de volume. Ils augmentent fortement pour M = Pd et légèrement pour M = Cu, tandis qu'elles diminuent pour M = Co. Les propriétés d'hydrogénation sont très sensibles à la nature chimique des substitutions. La capacité diminue fortement avec la substitution par Pd, modérément avec le Cu et reste stable pour le M = Co. Contrairement à l'effet attendu par des considérations géométrique, la substitution par Pd et par Cu diminuent la stabilité des hydrures. Les calculs DFT montrent qu'un effet électronique, et non géométrique, régit la stabilité des hydrures pour M = Pd. La substitution par le cobalt induit une formation de plusieurs hydrures par étapes successives, observée par mesure d'isothermes pression-composition en multiple plateaux. Pour les applications, la substitution de Ni par Cu avec une faible teneur (z = 0,2) augmente la capacité de décharge électrochimique de TiNi de 150 à 300 mAh/g en raison de la déstabilisation de l'hydrure. Cela ouvre de nouvelles perspectives pour l'utilisation d'alliages TiNi comme électrodes de batteries Ni-MH. En revanche, la substitution par Pd ou Cu (avec z = 0,5) est très efficace pour réduire la réactivité de TiNi avec l'hydrogène, et est donc intéressante pour des applications à mémoire de forme sous un environnement réducteur / The PhD thesis aims to improve shape memory and hydrogen storage properties of TiNi by chemical substitutions in the Ni sub-lattice. The effect of Pd, Cu and Co substitutions on crystal structure, martensitic transformation and hydrogenation properties of TiNi has been studied by structural (X-ray and neutron powder diffraction), calorimetric, solid-gas and electrochemical means. Ab initio DFT calculations were done to highlight electronic effects on hydrogenation properties. The three substitutions, TiNi1-zMz (M = Pd, Cu and Co; z ≤ 0.5), lead to the formation of pseudobinary compounds. Substitutions by Pd and Cu increase the unit-cell volume of TiNi, whereas the reverse effect occurs for Co. Martensitic transformation temperatures correlate with volume variations. They increase strongly for M = Pd and slightly for M = Cu, whereas M = Co decreases it. Hydrogenation properties are very sensitive to chemical elements substitution. The capacity decreases strongly for M = Pd, moderately for M = Cu and remains stable for M = Co. Contrary to expected effect by geometric model, both Pd and Cu substitutions decrease the stability of hydrides. DFT calculations show that electronic rather than geometric effects govern hydride stability for M = Pd. Co substitution induces step-wise formation of hydrides with a multi-plateau behaviour in pressure-composition isotherms. As concerns applications, low amount of Cu substitution (z =0.2) increases the electrochemical discharge capacity of TiNi from 150 to 300 mAh/g due to hydride destabilization. This opens new perspectives for using TiNi-based alloys in Ni-MH batteries. In contrast, Pd and high amount of Cu substitution (z = 0.5) are effective to decrease TiNi reactivity towards hydrogen, and therefore attractive for shape memory applications under reductive environment

Neste trabalho, avaliou-se inicialmente o efeito da substituição de elementos em ligas à base de LaMgAlMnCoNi do tipo AB5 com adição de estanho (Sn) e cobre (Cu) em substituição ao cobalto (Co), para utilização em ligas absorvedoras de hidrogênio e em eletrodos negativos de baterias de Ni-HM. Avaliou-se a influência desta substituição na microestrutura do material. Notou-se que o aumento da concentração de estanho promove a formação da fase LaNiSn nas ligas, bem como a diminuição das duas fases principais: LaNi5 e (La,Mg)Ni3. Adicionalmente, utilizou-se o refinamento de Rietveld para quantificar as fases em cada composição. Posteriormente, propôs-se um estudo da absorção de hidrogênio. Notou-se que a liga com cobalto apresentou a melhor capacidade de absorção de hidrogênio. Ademais, verificou-se o comportamento destas ligas na capacidade de descarga, estabilidade cíclica e na alta taxa de descarga de baterias de Ni-HM. A maior capacidade de descarga medida foi para a liga de cobalto, atingindo 337,1 mAh/g. Notou-se, posteriormente uma melhora na estabilidade cíclica das baterias com o aumento do teor de cobre. Além disso, observou-se que a alta taxa de descarga apresenta melhores valores com a adição de cobre na composição. Por fim, avaliou-se o efeito da susceptibilidade a corrosão. Notou-se que o estanho promove um aumento na resistência à corrosão das ligas em eletrólito alcalino. / In this work, it has firstly been evaluated the effect of tin (Sn) and copper (Cu) substituting cobalt (Co) in LaMgAlMnCoNi AB5-type alloys for use in hydrogen storage materials and negative electrodes of Ni-MH batteries. The influence of this substitution on the microstructure of these materials has been evaluated. It could be noted that increasing the tin concentration promotes the formation of LaNiSn phase and decrease of two main phases of these alloys: LaNi5 and (La,Mg)Ni3. Additionally, the Rietveld refinement has been evaluated to quantify phases in each composition. Subsequently, it has been proposed a study of the hydrogen absorption in these alloys. It could be observed that the cobalt alloy showed the best hydrogen absorption capacity. Moreover, the behavior of these alloys has been investigated in the discharge capacity, cyclic stability and high rate dischargeability of Ni-MH batteries. The highest discharge capacity has been measured for cobalt alloy, reaching 337.1 mAh/g. It has been noted, further improvement in the cyclic stability batteries with increasing copper content in the alloys. Furthermore, it has been observed that the high rate dischargeability has better values with the addition of copper in the composition. Finally, it has been evaluated the effect of susceptibility to corrosion. It has been noted that tin promotes an increase in corrosion resistance of the alloys in an alkaline electrolyte.

Les accumulateurs Ni-MH (Nickel-Métal-Hydrure) sont un sujet prometteur et largement étudié dans les recherches d’une énergie propre et durable. Trouver le matériau idéal pour l'électrode négative à haute densité volumétrique et gravimétrique est la clé pour l’application de cette technologie. Les hydrures métalliques à base de Ti-Ni ont des propriétés équilibrées entre la capacité d’hydrogène et les performances électrochimiques.L’objectif de cette thèse est d’étudier les effets de substitutions/additions d’éléments et de la mécanosynthèse sur la structure et les propriétés d’hydrogène des alliages Ti-Ni. Dans cette étude, une série d’alliages à base de Ti-Ni avec des substitutions/additions de Mg ou de Zr ont été systématiquement étudiés.Les alliages (TiNi)1-xMgx, (TiH2)1.5Mg0.5Ni, and Ti2-xZrxNi ont été synthétisés par mécanosynthèse à partir de poudres élémentaires. Dans un premier temps, l’influence du temps de broyage et les effets de substitutions/additions sur les microstructures ont été caractérisés par des techniques telles que la DRX, le MEB et le MET. Dans un second temps, les propriétés d’hydrogénation des différents alliages ont été mesurées par des réactions solid-gaz et par cyclage électrochimique.La théorie de la fonctionnelle de la densité (DFT) en utilisant le programme CASTEP a permis de calculer les enthalpies de formation afin de comparer la stabilité thermodynamique des alliages obtenus. Dans ces travaux de recherche, nous avons identifié les priorités d’alliage des ternaires Ni-Ti-Mg et Ti-Ni-Zr dans des conditions de broyage. La transformation structurale du Ti en phase CFC, induite par l’introduction d’éléments étrangers, a été mise en évidence.Les courbes PCI (Pression-Composition-Isothermes) et les capacités de décharge en fonction du nombre de cycles indiquent les propriétés d’hydrogène des alliages obtenus, y compris TiNi, Ti2Ni (amorphe), Ti-Mg et Ti-Zr. / Ni-MH (Nickel-Metal-Hydride) batteries have been a promising and extensively studied topic among clean and sustainable energy researches. Finding the ideal material for the negative electrode with high volumetric and gravimetric densities is the key to apply this technology on broader applications. Metal hydrides based on Ti-Ni have balanced properties between hydrogen capacity and electrochemical performances in cycling.The objective of this thesis is to study the effects of element substitution/doping and mechanical alloying on the structural and hydrogen properties of Ti-Ni alloys. In this study, a series of Ti-Ni based systems with Mg or Zr doping/substitution have been systematically investigated.The metallic compounds (TiNi)1-xMgx, (TiH2)1.5Mg0.5Ni, and Ti2-xZrxNi were synthesized by mechanically alloying from elemental powders.The milling time and effects of Mg, Zr substitution/doping were studied firstly in respect of their microstructures, using characterization techniques including XRD, SEM, TEM (EDX support), followed by the hydrogen properties measurements of the samples by hydrogen solid-gas reaction and electrochemical cycling.A first principle calculation tool based on DFT (Density Functional Theory) was carried out to further investigate the enthalpy of formation in order to compare the thermodynamical stability of the obtained compounds. In the study, we have found the alloying priorities in the ternary alloys Ti-Ni-Mg and Ti-Ni-Zr under milling conditions.A structure transformation of Ti to FCC induced by foreign elements is reported and investigated. Enthalpy of formation per atom of the compounds were obtained by DFT calculations, which helped interpreting the experimental results. PCI (Pressure Composition Isotherms) curves and discharge capacities as the function of cycling numbers revealed the hydrogen properties of the obtained compounds, including TiNi, Ti2Ni (amorphous), Ti-Mg and Ti-Zr.

Le stockage de l'hydrogène est l'un des plus grands problèmes techniques qui restreignent l'application pratique de l'hydrogène. Les hydrures métalliques sont considérés comme la solution principale à ce problème puisqu'ils peuvent absorber et désorber de façon réversible une grande quantité d'hydrogène sous une température et une pression modérées. Par ailleurs, les hydrures métalliques utilisés comme électrodes négatives dans les accumulateurs Nickel-Métal Hydrure (Ni-MH) sont également les composants clés des performances de ces derniers.Dans cette thèse, les alliages métalliques TiMgNix, MgTi1-xNix et TiMg1-xNix ont été synthétisés par broyage mécanique à partir de poudres élémentaires. La microstructure et les transformations de phase des échantillons préparés ont été caractérisées par DRX, MEB et MET (avec microanalyse EDS).Les propriétés d'hydrogénation ont été mesurées par réaction d'hydrogène solide-gaz et par des essais électrochimiques. Un diagramme de composition-capacité 3D a été établi sur la base du diagramme de phase ternaire Ti-Mg-Ni. Un procédé de broyage en deux étapes a été mis en œuvre pour améliorer les performances électrochimiques des alliages Ti-Mg-Ni.De plus, les alliages TiNi1-xCux ont été synthétisés par broyage mécanique et ensuite recuits. L 'influence de la substitution du nickel par le cuivre sur la structure et les propriétés électrochimiques est étudiée en utilisant une double approche: expérimentale et par simulation.Les résultats obtenus par la théorie de la fonctionnelle de la densité (DFT) en utilisant le programme CASTEP montrent que l'enthalpie de formation et l'énergie d'adsorption de l¿hydrogène de la phase pseudo-binaire Ti(Ni, Cu) sont en bon accord avec les résultats expérimentaux. / The storage of hydrogen is one of the biggest technical problem that restrict the practical application of hydrogen. Metal hydrides are mainly regarded as the solution facing to this issue since it can reversibly absorb and desorb big amount of hydrogen under moderate temperature and pressure. Meanwhile, metal hydrides used as the negative electrodes of Ni-MH batteries are also the key components to the battery performance.In this thesis, the metallic composite TiMgNix, MgTi1-xNix and TiMg1-xNix were synthesized by mechanical alloying from elemental powder. The microstructure and phase transformation of prepared samples were characterized by XRD, SEM, TEM (EDS support). The hydrogenation properties were measured by hydrogen solid-gas reaction and electrochemical tests. Based on the Ti-Mg-Ni ternary phase diagram, a 3D composition-capacity diagram have been established. Two-step mill process was proposed for meliorating the electrochemical performance of Ti-Mg-Ni alloys.Additionally, TiNi1-xCux alloys had been synthesized by mechanical alloying and subsequent annealing and studied using experimental and computational approaches. The influence of Cu substitution for Ni on the phase structure and electrochemical properties are investigated. The first principle calculation was carried out to study the formation enthalpy and hydrogen adsorption energy of pseudo-binary Ti(Ni, Cu) phase. The computational results are in good agreement with experimental results.

Neste trabalho, avaliou-se inicialmente o efeito da substituição de elementos em ligas à base de LaMgAlMnCoNi do tipo AB5 com adição de estanho (Sn) e cobre (Cu) em substituição ao cobalto (Co), para utilização em ligas absorvedoras de hidrogênio e em eletrodos negativos de baterias de Ni-HM. Avaliou-se a influência desta substituição na microestrutura do material. Notou-se que o aumento da concentração de estanho promove a formação da fase LaNiSn nas ligas, bem como a diminuição das duas fases principais: LaNi5 e (La,Mg)Ni3. Adicionalmente, utilizou-se o refinamento de Rietveld para quantificar as fases em cada composição. Posteriormente, propôs-se um estudo da absorção de hidrogênio. Notou-se que a liga com cobalto apresentou a melhor capacidade de absorção de hidrogênio. Ademais, verificou-se o comportamento destas ligas na capacidade de descarga, estabilidade cíclica e na alta taxa de descarga de baterias de Ni-HM. A maior capacidade de descarga medida foi para a liga de cobalto, atingindo 337,1 mAh/g. Notou-se, posteriormente uma melhora na estabilidade cíclica das baterias com o aumento do teor de cobre. Além disso, observou-se que a alta taxa de descarga apresenta melhores valores com a adição de cobre na composição. Por fim, avaliou-se o efeito da susceptibilidade a corrosão. Notou-se que o estanho promove um aumento na resistência à corrosão das ligas em eletrólito alcalino. / In this work, it has firstly been evaluated the effect of tin (Sn) and copper (Cu) substituting cobalt (Co) in LaMgAlMnCoNi AB5-type alloys for use in hydrogen storage materials and negative electrodes of Ni-MH batteries. The influence of this substitution on the microstructure of these materials has been evaluated. It could be noted that increasing the tin concentration promotes the formation of LaNiSn phase and decrease of two main phases of these alloys: LaNi5 and (La,Mg)Ni3. Additionally, the Rietveld refinement has been evaluated to quantify phases in each composition. Subsequently, it has been proposed a study of the hydrogen absorption in these alloys. It could be observed that the cobalt alloy showed the best hydrogen absorption capacity. Moreover, the behavior of these alloys has been investigated in the discharge capacity, cyclic stability and high rate dischargeability of Ni-MH batteries. The highest discharge capacity has been measured for cobalt alloy, reaching 337.1 mAh/g. It has been noted, further improvement in the cyclic stability batteries with increasing copper content in the alloys. Furthermore, it has been observed that the high rate dischargeability has better values with the addition of copper in the composition. Finally, it has been evaluated the effect of susceptibility to corrosion. It has been noted that tin promotes an increase in corrosion resistance of the alloys in an alkaline electrolyte.