abstract: Metal hydride materials have been intensively studied for hydrogen storage applications. In addition to potential hydrogen economy applications, metal hydrides offer a wide variety of other interesting properties. For example, hydrogen-dominant materials, which are hydrides with the highest hydrogen content for a particular metal/semimetal composition, are predicted to display high-temperature superconductivity. On the other side of the spectrum are hydrides with small amounts of hydrogen (0.1 - 1 at.%) that are investigated as viable magnetic, thermoelectric or semiconducting materials. Research of metal hydride materials is generally important to gain fundamental understanding of metal-hydrogen interactions in materials. Hydrogenation of Zintl phases, which are defined as compounds between an active metal (alkali, alkaline earth, rare earth) and a p-block metal/semimetal, were attempted by a hot sintering method utilizing an autoclave loaded with gaseous hydrogen (< 9 MPa). Hydride formation competes with oxidative decomposition of a Zintl phase. The oxidative decomposition, which leads to a mixture of binary active metal hydride and p-block element, was observed for investigated aluminum (Al) and gallium (Ga) containing Zintl phases. However, a new phase Li2Al was discovered when Zintl phase precursors were synthesized. Using the single crystal x-ray diffraction (SCXRD), the Li2Al was found to crystallize in an orthorhombic unit cell (Cmcm) with the lattice parameters a = 4.6404(8) &Aring;, b = 9.719(2) &Aring;, and c = 4.4764(8) &Aring;. Increased demand for materials with improved properties necessitates the exploration of alternative synthesis methods. Conventional metal hydride synthesis methods, like ball-milling and autoclave technique, are not responding to the demands of finding new materials. A viable alternative synthesis method is the application of high pressure for the preparation of hydrogen-dominant materials. Extreme pressures in the gigapascal ranges can open access to new metal hydrides with novel structures and properties, because of the drastically increased chemical potential of hydrogen. Pressures up to 10 GPa can be easily achieved using the multi-anvil (MA) hydrogenations while maintaining sufficient sample volume for structure and property characterization. Gigapascal MA hydrogenations using ammonia borane (BH3NH3) as an internal hydrogen source were employed in the search for new hydrogen-dominant materials. Ammonia borane has high gravimetric volume of hydrogen, and additionally the thermally activated decomposition at high pressures lead to a complete hydrogen release at reasonably low temperature. These properties make ammonia borane a desired hydrogen source material. The missing member Li2PtH6 of the series of A2PtH6 compounds (A = Na to Cs) was accessed by employing MA technique. As the known heavier analogs, the Li2PtH6 also crystallizes in a cubic K2PtCl6-type structure with a cell edge length of 6.7681(3) &Aring;. Further gigapascal hydrogenations afforded the compounds K2SiH6 and Rb2SiH6 which are isostructural to Li2PtH6. The cubic K2SiH6 and Rb2SiH6 are built from unique hypervalent SiH62- entities with the lattice parameters of 7.8425(9) and 8.1572(4) &Aring;, respectively. Spectroscopic analysis of hexasilicides confirmed the presence of hypervalent bonding. The Si-H stretching frequencies at 1550 cm-1 appeared considerably decreased in comparison with a normal-valent (2e2c) Si-H stretching frequencies in SiH4 at around 2200 cm-1. However, the observed stretching modes in hypervalent hexasilicides were in a reasonable agreement with Ph3SiH2- (1520 cm-1) where the hydrogen has the axial (3e4c bonded) position in the trigoal bipyramidal environment. / Dissertation/Thesis / Ph.D. Chemistry 2013

Neste trabalho eletrodos negativos de baterias de níquel-hidreto metálico constituídos por ligas de hidreto metálico baseadas em MgNi, processadas por moagem de alta energia utilizando-se um moinho de bolas tipo vibratório, foram preparadas e inicialmente investigadas utilizando técnicas como difração de raios-X, energia dispersiva de raios-X, microscopia eletrônica de transmissão e microscopia eletrônica de varredura para caracterização estrutural e morfológica. Em seguida foram feitos estudos eletroquímicos como ciclos galvanostáticos de carga e descarga e voltametria cíclica para se obter informações como a estabilidade e a capacidade de descarga da liga, bem como conhecer os processos de difusão que ocorrem no interior das ligas. As ligas foram baseadas em Mg55Ni45 com o Mg sendo substituído parcialmente por Ti em até 8% atômico e o Ni substituído parcialmente por Pt ou por Pd em até 4%, em cada um dos casos. As análises consistiram em avaliar ligas com 1 ou 2 substituintes, gerando uma série de combinações devidas às variações na quantidade de cada substituinte. Foi observado que as ligas contendo Ti apresentaram melhora na capacidade de descarga inicial quando comparadas à liga base; ligas contendo Pt ou Pd melhoraram a capacidade de reter carga durante os ciclos, apresentando maior estabilidade; ligas contendo Ti e Pt apresentam melhores capacidades de descarga inicial, inclusive maiores que as ligas contendo Ti, finalmente as ligas contendo Pd apresentaram as maiores capacidades, com e sem adição de Ti. / This work investigated negative electrodes for nickel-metal hydride batteries, formed by Mg-based metal hydride alloys and prepared by high energy mechanical alloying. The prepared alloys were first characterized using X-ray diffraction, energy dispersive X-ray analyses, transmission electron microscopy and scanning electron microscopy, for obtaining structural and morphological information\'s of the materials. Electrochemical analyses comprised galvanostatic charge/discharge cycling and cyclic voltammetry, used for obtaining information\'s on the alloy discharge capacity and stability as well as on the diffusion processes occurring in the bulk of the alloys. The alloys were based on Mg55Ni45, in which Mg was partially substituted by Ti up to 8 % (atomic) and Ni partially substituted by Pt or Pd up to 4 % (atomic). These materials were formed with 1 or 2 substituting elements, in a series of several Ti, Pt, Pd, Ti and Pt and Ti and Pd combinations. It was seen the alloys containing Ti show higher initial discharge capacity when compared to the base material. In the case where Pt or Pd substitutes Ni, higher charge retention capacity along the cycles was seen, but when Ti and Pt or Pd are used together, the alloys show higher initial discharge capacity, larger than when Ti used alone. Finally, it was seen that the alloys containing Pd present the largest discharge capacity, both in the absence or in the presence of Ti.

Neste trabalho foi feito um estudo das propriedades estruturais e eletroquímicas de eletrodos formados por pó de liga de hidreto metálico Zr0,9Ti0,1Ni1,04Mn0,64V0,46 (tipo AB2) preparadas em forno a arco e tratadas por moagem em moinho de bolas na presença de pó de Ni ou da liga LaNi4,7Sn0,3. Também foram estudadas ligas à base de Mg-Ni preparadas por moagem de alta energia, com e sem a inclusão de um terceiro elemento (Ti ou Pt). Neste último caso, foi realizada deposição eletroquímica para o revestimento da superfície da liga Mg-Ni com paládio. Os estudos nos dois sistemas foram conduzidos utilizando-se as técnicas de EDX (energia dispersiva de raios X), DRX (difração de raios X) e MEV (microscopia eletrônica de varredura) para a caracterização física dos materiais. Também foram realizados experimentos espectroscopia de absorção de raios X (XAS) e de microscopia eletrônica de transmissão (MET). Os estudos eletroquímicos incluíram medidas da polarização dos eletrodos ao longo dos ciclos de carga/descarga, com o monitoramento da capacidade de descarga em função do número de ciclos. Medidas de espectroscopia de impedância eletroquímica em diferentes estado de carga, temperaturas e números de ciclos foram realizadas nos eletrodos formados com as diferentes ligas. Foi observado que a capacidade de armazenamento de carga da liga AB2 sem tratamento, aumenta muito lentamente com o decorrer do número de ciclos de carga/descarga, enquanto que os eletrodos formados com essa mesma liga, porém submetida aos tratamentos superficiais pela moagem com os diferentes aditivos, apresentam ativação muito mais rápida. Pelas medidas de impedância eletroquímica, observou-se alta similaridade da cinética reacional nas várias amostras AB2 analisadas. A substituição parcial da liga MgNi pela Pt levou à uma maior estabilidade aos ciclos de carga e descarga, inibindo a formação de hidróxido de Mg e proporcionando uma cinética tanto de absorção quanto de dessorção do hidreto maior que sua correspondente liga base. A eletrodeposição de Pd nestas ligas, leva à um incremento adicional na estabilidade do eletrodo. / This work reports results of studies on the structure and electrochemical properties of hydrogen storage alloy electrodes, formed by Zr0,9Ti0,1Ni1,04Mn0,64V0,46 (AB2-type), prepared in arc furnace and processed by ball milling in the presence of Ni and/or LaNi4,7Sn0,3 powder additives. The Mg- Ni based alloys with and without incorporation of Ti and Pt, processed by mechanical alloying were also investigated. In this case, electrochemical deposition of palladium was carried out on the surface of Mg-Ni based alloy particles aiming at improving the alloy stability. The structure of all materials were characterized by energy dispersive X-ray (EDS) analyses, X-ray diffraction (XRD) and scanning electronic microscopy (SEM). X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) were also employed for this purpose. Electrochemical studies involved measurements of the electrode polarization along the charge/discharge cycles and also monitoring total discharge capacity as a function of the cycle number. Reaction kinetics were investigated by electrochemical impedance spectroscopy (EIS) measurements, conducted at different states of charge, temperatures and cycle numbers for the different metal hydride electrodes. It was found that the charge storage capacity increased very slowly along the initial charge/discharge cycles for the bare AB2 alloy, but a significant decrease of the activation time, due to a raise on the active area caused by the milling treatment was seen, independent of the additive nature. Electrochemical impedance showed similar reaction kinetics for different AB2 samples. The inclusion of small content of Pt in the Mg-Ni alloy leaded to a significant increase of the material stability for the charge/discharge cycles, probably because of a reduction in the corrosion processes. Consistently, the electrochemical coatings of Pd lead to a raise in the cycling stability of these alloys.

Les batteries lithium-ion sont aujourd’hui très utilisées pour alimenter l’électronique portable telle que les ordinateurs, les smartphones et les caméras. Cependant, de nouvelles applications telles que les véhicules électriques et les systèmes stationnaires de stockage d'énergie nécessitent des batteries à performances améliorées. En particulier, de nouveaux matériaux d'électrode avec des densités d'énergie plus élevées sont requis. Les hydrures de MgH2 et TiH2 et leurs mélanges possèdent de très fortes capacités électrochimiques (>1 Ah/g). Ils ont été étudiés comme matériaux d’électrode négative dans les batteries Li-ion. La réaction de conversion de ces hydrures avec du lithium et les changements structuraux induits ont été étudiés en détails pour mieux comprendre les mécanismes réactionnels et leur réversibilité. Les propriétés électrochimiques de couches minces de MgH2 et des poudres composites de MgH2+TiH2 ont été étudiées en utilisant à la fois des électrolytes organiques liquides et un électrolyte solide LiBH4. La capacité réversible et la tenue au cyclage dépendent fortement du rapport molaire entre les deux hydrures et des conditions de cyclage. Le transport de masse et la densité d’interfaces à l'intérieur de l'électrode sont identifiés comme les principaux facteurs affectant la réversibilité de la réaction de conversion / Today, lithium-ion batteries are widely used as power supplies in portable electronics such as laptops, smartphones and cameras. However, new applications such as full electric vehicles and energy storage stationary systems require enhanced battery performances. In particular, novel electrode materials with higher energy density are needed.MgH2 and TiH2 hydrides and mixtures of them have high electrochemical capacity (> 1 Ah/g). They have been studied as negative electrode materials in Li-ion batteries. The conversion reaction of lithium with these hydrides and the related microstructural changes have been deeply investigated to gain a better understanding of reaction mechanisms and their reversibility. The electrochemical properties of MgH2 thin films and MgH2+TiH2 composite powders have been evaluated using both liquid organic and solid (LiBH4) electrolytes. Reversible capacity and cycle-life are found to strongly depend on both molar ratio between the hydrides and cycling conditions. Mass transport and density of interfaces within the electrode are identified as the main factors affecting the reversibility of the conversion reaction

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20368号 / 工博第4305号 / 新制||工||1667(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 乾 晴行, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Este trabalho teve por objetivo a pesquisa e o desenvolvimento de catalisadores formados por ligas formadoras de hidreto metálico (LaNi4,7Sn0,2Cu0,1, LaNi4,78Al0,22, LaNi4,78Mn0,22 e LaNi4,7Sn0,2Co0,1), com e sem depósitos de metais nobres (Pt, Au, Pd), para uso no ânodo de células a combustível alcalinas. Buscou-se o entendimento do mecanismo da reação de oxidação de boroidreto de sódio em meio alcalino nestes diferentes materiais em diferentes configurações de eletrodos e em diversas concentrações de boroidreto. As ligas foram preparadas pelo método de fusão em forno a arco e os metais nobres foram depositados por troca galvânica. A caracterização físico-composicional foi feita por energia dispersiva de raios X (EDS), análise elementar, difração de raios X (DRX) e microscopia eletrônica de transmissão (MET). Já a caracterização eletroquímica foi feita por voltametria cíclica, curvas de capacidade de descarga, curvas de polarização e espectrometria de massas eletroquímica online (OLEMS). Os resultados mostraram que a quantidade de material nobre presente nas ligas foi da ordem de 0,1 a 0,3 % e suas composições e organizações estruturais foram investigadas por EDS, DRX e MET. Os resultados eletroquímicos mostraram que o estado de hidretação da liga base é um fator importante na definição da cinética da reação de oxidação de boroidreto e que a extensão da formação de hidreto é dependente da velocidade do processo de hidrólise dos íons boroidreto, da capacidade da liga em estocar hidrogênio e da cinética de difusão dos átomos de hidrogênio atômico no interior das ligas. A atividade para a reação direta de oxidação de boroidreto foi baixa para as ligas que não continham em suas composições os metais nobres, entretanto a taxa de hidrólise para estes foi menor e a capacidade de armazenamento de hidrogênio foi maior. Os resultados também mostraram, para todas as diferentes composições, que as ligas podem ser carregadas com hidrogênio atômico tanto eletroquimicamente quanto pela exposição à solução de boroidreto. Foi observado que houve contínua hidretação de todas as ligas durante ensaios cronoamperométricos na presença de boroidreto. Esses fenômenos indicaram que a liga LaNi4.7Sn0.2Cu0.1 sem a deposição de metais nobres é a mais indicada para uma futura aplicação em um sistema DBFC/MHB (célula a combustível de boroidreto direto/bateria de hidreto metálico). / This work provides insights into the processes involved in the borohydride oxidation reaction (BOR) and hydrogen oxidation reaction in alkaline media on metal hydride alloys formed by LaNi4.7Sn0.2Cu0.1 and LaNi4.78Al0.22 with and without deposited Pt, Pd and Au, LaNi4,78Mn0,22 and LaNi4,7Sn0,2Co0,1. Measurements of BET, TEM, in situ XRD, DRIFTS, RRDE (gold ring) and OLEMS were made with the aim to characterize all the materials by different methodologies. The present investigation showed that the state of hydriding of LaNi4.7Sn0.2Cu0.1 and LaNi4.78Al0.22 is important in defining the kinetics and outcome of the BOR at these materials. The extent of hydride formation has been shown to depend on the rate of the BH4- hydrolysis, the hydrogen storage capacity of the alloy, and kinetics of H atom diffusion inside the alloy. The activity for the direct BOR is low in both bare metal hydride alloys, but the rate of the BH4- hydrolysis and the hydrogen storage capacity are higher, while the rate of H diffusion is slower in the bare LaNi4.78Al0.22. Results have shown that both the bare and all the noble metal modified alloys can be hydrided either electrochemically or by exposure to BH4- solutions, although for the LaNi4.78Al0.22-based materials the extent of this phenomenon is smaller. A continuous hydriding of all LaNi4.7Sn0.2Cu0.1-based and the bare LaNi4.78Al0.22 alloys are observed in the chronoamperometric BH4- oxidation measurements at low current densities. Addition of Pt on both alloys resulted in an increase of the BH4- hydrolysis, but the H2 formed is rapidly oxidized, confirming the initial predictions for this noble metal. In addition, the rates of the alloy hydriding/de-hydriding were not significantly affected by the presence of Pt, but this was not the case for Pd and Au, for which there was a drastic reduction of the rate of these processes. In the case of gold some increase of the BH4- hydrolysis is observed, although its presence does not change significantly the performances of the bare alloys. It was possible to confirm the formation of BH3OH- for all the samples by RRDE measurements, however for LaNi4.7Sn0.2Cu0.1 the formation of this product was lower compared to the other samples. Results showed that the first step of the electrode process is the hydriding of alloy by the hydrogen formed in the BH4- hydrolysis. The in situ XRD results have shown that the method of charging of the alloy, electrochemical or chemical, leads to different phase predominance and different site occupancies, but both methods lead to almost the same discharge capacity. In the electrolysis process, the &alpha;-&beta; phase transition is predominant while in the chemical charging by the exposure to borohydride solution the &alpha;-&beta; phase transition is more important. The results have also shown that the alloys with and without Pt lead essentially to the same phenomena, either with respect to the alloy structure and the electrochemical characteristics. All these phenomena point to the bare LaNi4.7Sn0.2Cu0.1 as a more adequate alloy system for applications in DBFC/MHB batteries.

Este trabalho teve por objetivo a pesquisa e o desenvolvimento de catalisadores formados por ligas formadoras de hidreto metálico (LaNi4,7Sn0,2Cu0,1, LaNi4,78Al0,22, LaNi4,78Mn0,22 e LaNi4,7Sn0,2Co0,1), com e sem depósitos de metais nobres (Pt, Au, Pd), para uso no ânodo de células a combustível alcalinas. Buscou-se o entendimento do mecanismo da reação de oxidação de boroidreto de sódio em meio alcalino nestes diferentes materiais em diferentes configurações de eletrodos e em diversas concentrações de boroidreto. As ligas foram preparadas pelo método de fusão em forno a arco e os metais nobres foram depositados por troca galvânica. A caracterização físico-composicional foi feita por energia dispersiva de raios X (EDS), análise elementar, difração de raios X (DRX) e microscopia eletrônica de transmissão (MET). Já a caracterização eletroquímica foi feita por voltametria cíclica, curvas de capacidade de descarga, curvas de polarização e espectrometria de massas eletroquímica online (OLEMS). Os resultados mostraram que a quantidade de material nobre presente nas ligas foi da ordem de 0,1 a 0,3 % e suas composições e organizações estruturais foram investigadas por EDS, DRX e MET. Os resultados eletroquímicos mostraram que o estado de hidretação da liga base é um fator importante na definição da cinética da reação de oxidação de boroidreto e que a extensão da formação de hidreto é dependente da velocidade do processo de hidrólise dos íons boroidreto, da capacidade da liga em estocar hidrogênio e da cinética de difusão dos átomos de hidrogênio atômico no interior das ligas. A atividade para a reação direta de oxidação de boroidreto foi baixa para as ligas que não continham em suas composições os metais nobres, entretanto a taxa de hidrólise para estes foi menor e a capacidade de armazenamento de hidrogênio foi maior. Os resultados também mostraram, para todas as diferentes composições, que as ligas podem ser carregadas com hidrogênio atômico tanto eletroquimicamente quanto pela exposição à solução de boroidreto. Foi observado que houve contínua hidretação de todas as ligas durante ensaios cronoamperométricos na presença de boroidreto. Esses fenômenos indicaram que a liga LaNi4.7Sn0.2Cu0.1 sem a deposição de metais nobres é a mais indicada para uma futura aplicação em um sistema DBFC/MHB (célula a combustível de boroidreto direto/bateria de hidreto metálico). / This work provides insights into the processes involved in the borohydride oxidation reaction (BOR) and hydrogen oxidation reaction in alkaline media on metal hydride alloys formed by LaNi4.7Sn0.2Cu0.1 and LaNi4.78Al0.22 with and without deposited Pt, Pd and Au, LaNi4,78Mn0,22 and LaNi4,7Sn0,2Co0,1. Measurements of BET, TEM, in situ XRD, DRIFTS, RRDE (gold ring) and OLEMS were made with the aim to characterize all the materials by different methodologies. The present investigation showed that the state of hydriding of LaNi4.7Sn0.2Cu0.1 and LaNi4.78Al0.22 is important in defining the kinetics and outcome of the BOR at these materials. The extent of hydride formation has been shown to depend on the rate of the BH4- hydrolysis, the hydrogen storage capacity of the alloy, and kinetics of H atom diffusion inside the alloy. The activity for the direct BOR is low in both bare metal hydride alloys, but the rate of the BH4- hydrolysis and the hydrogen storage capacity are higher, while the rate of H diffusion is slower in the bare LaNi4.78Al0.22. Results have shown that both the bare and all the noble metal modified alloys can be hydrided either electrochemically or by exposure to BH4- solutions, although for the LaNi4.78Al0.22-based materials the extent of this phenomenon is smaller. A continuous hydriding of all LaNi4.7Sn0.2Cu0.1-based and the bare LaNi4.78Al0.22 alloys are observed in the chronoamperometric BH4- oxidation measurements at low current densities. Addition of Pt on both alloys resulted in an increase of the BH4- hydrolysis, but the H2 formed is rapidly oxidized, confirming the initial predictions for this noble metal. In addition, the rates of the alloy hydriding/de-hydriding were not significantly affected by the presence of Pt, but this was not the case for Pd and Au, for which there was a drastic reduction of the rate of these processes. In the case of gold some increase of the BH4- hydrolysis is observed, although its presence does not change significantly the performances of the bare alloys. It was possible to confirm the formation of BH3OH- for all the samples by RRDE measurements, however for LaNi4.7Sn0.2Cu0.1 the formation of this product was lower compared to the other samples. Results showed that the first step of the electrode process is the hydriding of alloy by the hydrogen formed in the BH4- hydrolysis. The in situ XRD results have shown that the method of charging of the alloy, electrochemical or chemical, leads to different phase predominance and different site occupancies, but both methods lead to almost the same discharge capacity. In the electrolysis process, the &alpha;-&beta; phase transition is predominant while in the chemical charging by the exposure to borohydride solution the &alpha;-&beta; phase transition is more important. The results have also shown that the alloys with and without Pt lead essentially to the same phenomena, either with respect to the alloy structure and the electrochemical characteristics. All these phenomena point to the bare LaNi4.7Sn0.2Cu0.1 as a more adequate alloy system for applications in DBFC/MHB batteries.

<p>Future energy systems based on hydrogen as energy carrier require reliable ways for storing hydrogen gas in safe, clean and efficient ways. Metal hydrides absorb hydrogen gas reversibly, making them suitable for storage applications. Investigations of the crystal structures of these materials contribute to an understanding of the factors which can influence the absorption<i>. </i></p><p>Three systems, Ti₃Sn-D, Nb₄MSi-D (M=Co or Ni) and Pd-Ni-P, have been investigated in this thesis. Various solid state synthesis techniques have been used for sample preparation. The crystal structures have been studied using x-ray and neutron diffraction techniques.</p><p>Three metal hydride phases were found in the Ti₃Sn-D system upon hydrogenation. Deuterium occupies titanium octahedra and the applied deuterium pressure induces the phase transitions. The distances between the deuterium atoms increase from 2.47 Å in orthorhombic Ti₃SnD_0.80 to 4.17 Å in cubic Ti₃SnD.</p><p>The Nb₄MSi-D system (M=Co or Ni) readily absorbs deuterium at room temperature and 90 kPa deuterium pressure to give a deuterium content of Nb₄MSiD_~2.5. Two interstitial voids, both coordinated by four niobium atoms arranged in a tetrahedral configuration, accommodate deuterium atoms. </p><p>Two ternary phases and a solid solution of nickel in Pd₃P have been synthesised and the crystal structures determined. PdNi₂P is orthorhombic and crystallises in the MgCuAl₂-type structure: an ordered derivative of the Re₃B-type structure. Pd₈Ni₃₁P₁₆ is a tetragonal high-temperature phase stable at 700°C with 110 atoms in the unit cell. Pd_2.7Ni_0.3P_0.94 has the cementite-type structure with mixed occupancy of palladium and nickel at one of the two non-equivalent crystallographic metal positions.</p>

Future energy systems based on hydrogen as energy carrier require reliable ways for storing hydrogen gas in safe, clean and efficient ways. Metal hydrides absorb hydrogen gas reversibly, making them suitable for storage applications. Investigations of the crystal structures of these materials contribute to an understanding of the factors which can influence the absorption. Three systems, Ti3Sn-D, Nb4MSi-D (M=Co or Ni) and Pd-Ni-P, have been investigated in this thesis. Various solid state synthesis techniques have been used for sample preparation. The crystal structures have been studied using x-ray and neutron diffraction techniques. Three metal hydride phases were found in the Ti3Sn-D system upon hydrogenation. Deuterium occupies titanium octahedra and the applied deuterium pressure induces the phase transitions. The distances between the deuterium atoms increase from 2.47 Å in orthorhombic Ti3SnD0.80 to 4.17 Å in cubic Ti3SnD. The Nb4MSi-D system (M=Co or Ni) readily absorbs deuterium at room temperature and 90 kPa deuterium pressure to give a deuterium content of Nb4MSiD~2.5. Two interstitial voids, both coordinated by four niobium atoms arranged in a tetrahedral configuration, accommodate deuterium atoms. Two ternary phases and a solid solution of nickel in Pd3P have been synthesised and the crystal structures determined. PdNi2P is orthorhombic and crystallises in the MgCuAl2-type structure: an ordered derivative of the Re3B-type structure. Pd8Ni31P16 is a tetragonal high-temperature phase stable at 700°C with 110 atoms in the unit cell. Pd2.7Ni0.3P0.94 has the cementite-type structure with mixed occupancy of palladium and nickel at one of the two non-equivalent crystallographic metal positions.