Puszkiel, Julián A. (2012) Preparación, estudio y optimización de hidruros complejos para almacenamiento de hidrógeno. / Preparation, study and optimization of complex hidrides for hydrogen storage. Tesis Doctoral en Ciencias de la Ingeniería, Universidad Nacional de Cuyo, Instituto Balseiro.
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Resumen en español
El hidrógeno es considerado un potencial vector energético porque es abundante, su oxidación produce agua y libera grandes cantidades de energía. Sin embargo, su utilización masiva como portador de energía no fue posible aún dado que existen inconvenientes tecnológicos que deben ser resueltos. La falta de disponibilidad de un medio seguro y eficiente para almacenar hidrógeno es uno de los principales problemas a resolver. En la presente tesis se investigaron materiales formadores de hidruros para el almacenamiento de hidrógeno. Los materiales fueron preparados por distintos procedimientos basados en la molienda mecánica (MM y MMR) y se utilizaron diversas técnicas para evaluar sus características microestructurales (XRD ex–situ e in–situ, SEM, EDS, PSD, XAFS y ASAXS), térmicas (DSC, HP-DSC y TG), termodinámicas y cinéticas (técnica volumétrica tipo Sieverts). En un comienzo, se estudiaron compuestos con distintas proporciones estequiométricas de Mg–Fe. Las propiedades termodinámicas como así también los mecanismos que limitan la velocidad de absorción y desorción de hidrógeno del sistema Mg–Fe–H fueron analizadas. La entalpía de absorción del sistema hidruro Mg–Fe–H corresponde la mezcla de hidruros MgH_2–Mg_2FeH_6 (~ 70 kJ/mol H_2), mientras que la entalpía de desorción presenta un valor para el MgH_2 (~ 70 kJ/mol H_2) y otro para el Mg_2FeH_6 (~ 90 kJ/mol H_2). Se encontró que un material en base magnesio compuesto por una relación estequiométrica 15Mg–Fe (Mg + 6,3 % mol Fe) y preparado por molienda en atmósfera de hidrógeno presenta capacidades de almacenamiento de hidrógeno de 5,0 % p/p a 350 ºC y estabilidad al ciclado. Mediante la aplicación de los modelos integrales gas–sólido, se obtuvo que la etapa limitante de la velocidad de absorción es la difusión de los átomos de hidrógeno a través de la capa hidruro. Además, se encontró también que la etapa limitante de la velocidad de desorción es el movimiento de la interfase metal/hidruro. Dadas las características del material 15Mg–Fe y con el fin de evitar la atmósfera reactiva de hidrógeno durante la molienda, se lo preparó por medio de la molienda mecánica en atmósfera inerte (Ar). El material obtenido sólo alcanzó capacidades de almacenamiento cercanas al 1,5 % p/p a 350 ºC y 2,0 MPa, debido a sus pobres características microestructurales luego del proceso de molienda. Sin embargo, al adicionar una pequeña cantidad de LiBH_4 al material 15Mg–Fe se observó una notable mejora en su microestructura luego del proceso de molienda en atmósfera inerte. Posteriormente, y por medio del agregado de haluros de hierro se obtuvieron capacidades de almacenamiento de hidrógeno superiores al 6,5 % p/p a 350 ºC (2,0 MPa) y 5,0 % p/p a 275 ºC (2,5 MPa). En base a resultados experimentales y mediante cálculos de las composiciones de las fases en el equilibrio, se obtuvo que las interacciones entre el LiBH_4 y los haluros de Fe (FeF_3 y FeCl_3) resultaron en la formación de boruro de hierro. Si bien se lograron materiales en base Mg con interesantes características para el almacenamiento de hidrógeno, las propiedades termodinámicas de los mismos corresponden a las del MgH_2. La estabilidad termodinámica dada por el fuerte enlace Mg–H no permite la liberación del hidrógeno a temperaturas por debajo de 300 ºC. Por esta razón y dadas las propicias propiedades termodinámicas (ΔH = 40,5 kJ.mol”-1 H_2, Td = 225 ºC a la presión atmosférica de 101,3 kPa) y la alta capacidad de almacenamiento de hidrógeno teórica (11,45 %p/p) de la reacción 2LiBH_4+MgH_2 ↔ 2LiH + MgB_2 + 4H_2, se la estudió con el agregado de aditivos en base hierro (Fe, Fe-isopropóxido, FeF_3 y FeCl_3). Se encontró el Fe es reducido a Fe metálico, ya sea durante el proceso de molienda o la interacción con el hidrógeno por la acción del LiH o LiBH_4. Esto resulta en menores capacidades de almacenamiento por la formación de compuestos como LiF y LiCl. El agregado de Fe como catalizador disminuye los tiempos requeridos principalmente para la desorción del material 2LiH + MgB_2 de 12 a 6 horas. Sin embargo, no se pudo reducir la temperatura de desorción de hidrógeno por debajo de 400 ºC. Resultados obtenidos por XAFS evidenciaron la formación de FeB, lo cual confirma los cálculos de las composiciones en el equilibrio. Mediante la técnica ASAXS se ha observado que la microestructura de las fases ricas en hierro se deteriora notablemente durante el ciclado en hidrógeno debido a su aglomeración. Dada la naturaleza química y estructural del FeB y las pobres características microestructurales del material, se obtuvieron lentas velocidades de absorción/desorción de hidrógeno. Se han logrado capacidades del 7,0 %p/p H (absorción de H_2 a 350 ºC y 5,0 MPa; desorción de H_2 a 400 ºC y 0,55 MPa) con un material compuesto por 2LiH + MgB_2 + 5mol%Fe. El estudio de los distintos sistemas formadores de hidruros (materiales en base Mg–Fe, Mg y 2LiBH_4+MgH_2) ha aportado al conocimiento de sus características microestructurales propiedades termodinámicas y cinéticas con vistas y al empleo tecnológico de los mismos en aplicaciones móviles.
Resumen en inglés
Hydrogen is regarded as a promising energy vector because it is abundant, its oxidation produces water and releases huge amounts of energy. Despite the fact that its practical application is not far away, there are many technological constraints yet to solve. One of the main constraints is the lack of a safe and efficient method to store hydrogen. In the present thesis, hydride forming materials for hydrogen storage were investigated. The materials were prepared by mechanical milling procedures (MM and MMR). Several techniques were applied to evaluate their microstructural characteristics (XRD ex–situ and in– situ, SEM, EDS, PSD, XAFS and ASAXS), thermal behavior (DSC, HP-DSC and TG) and thermodynamic and kinetic properties (Sieverts technique). At the beginning, different stoichiometric compositions of Mg–Fe materials were studied. The thermodynamic behavior and hydrogen absorption mechanisms of the Mg–Fe–H system were characterized. The absorption enthalpy of the Mg–Fe–H hydride system belongs to the MgH_2–Mg_2FeH_6 mixture (~ 70 kJ/mol H_2). On the other hand, the Mg–Fe–H hydride system exhibits two desorption enthalpies. One corresponds to the MgH_2 (~ 70 kJ/mol H_2) and the other to the Mg_2FeH_6 (~ 90 kJ/mol H_2). It was found that a material composed of 15Mg–Fe (Mg + 6.3 mol % Fe) prepared by reactive mechanical milling (H_2) exhibits capacities of about 5.0 wt% H at 350 ºC and 2.0 MPa and cycling stability. In order to avoid the H2 atmosphere during milling, the 15Mg–Fe material was prepared by mechanical milling under inert atmosphere (Ar). The obtained material just reached 1.5 wt% H at 350 ºC and 2.0 MPa owing to its poor microstructural characteristics. However, adding tiny amounts of LiBH4 to the 15Mg–Fe material led to a noticeable improvement in the degree of microstructural refinement. Hence, through the addition of iron halides capacities of about 6.5 wt% H at 350 ºC (2.0 MPa) and 5.0 wt% H at 275 ºC (2.5 MPa) were reached. Based on experimental results and equilibrium calculations, the LiBH_4 and Fe halides (FeF_3 and FeCl_3) resulted in the formation of a Fe boride compound. Despite the fact that Mg based materials with interesting hydrogen storage characteristics were obtained, their thermodynamic behavior still belongs to MgH_2. The MgH_2 thermodynamic stability is conferred by the strong Mg–H bond and it does not allow reaching reversible hydrogen capacities of 7.6 wt% H (theoretical capacity of MgH_2) at temperatures below 300 ºC. For this reason and due to the proper theoretical thermodynamic stability (ΔH = 40.5 kJ.mol"-1 H_2, Td= 225 ºC at atmospheric pressure, 101.3 kPa) and the high theoretical gravimetric capacity (11.45 wt % H) of the reaction 2LiBH_4+MgH_2 ↔ 2LiH + MgB_2 + 4H_2, materials composed of 2LiBH_4 + MgH_2 (2LiH + MgB_2) plus Fe–based additives were studied (Fe, Fe-isopropoxide, FeF_3 and FeCl_3). It was found that the Fe-based additives are reduced to metallic Fe by either LiH or LiBH_4 during the milling process and hydrogen cycling. This led to lower hydrogen capacities and the loss of catalytic effect because of the formation of compounds such as LiF and LiCl. The addition of Fe noticeable reduces the desorption times from 12 to 6 hours. However, such effect does not remain upon further cycling. XAFS results confirm that FeB is formed during hydrogen cycling. ASAXS results suggest that upon cycling the iron rich nanoscale particles exhibit poor microstructural characteristics because of agglomeration. Thus, the presence of FeB, which is regarded as chemically inert, and the poor microstructural characteristics of the material result in slower hydrogen absorption–desorption rates. Hydrogen storage capacities of about 7.0 wt% H (absorption at 350 ºC and 5.0 MPa; desorption at 400 ºC and 0.55 MPa) were reached with a material composed of 2LiH + MgB_2 + 5 mol % Fe. The study of different hydride forming materials (Mg–Fe, Mg and 2LiBH_4+MgH_2 based materials) provides knowledge about their microstructural characteristics, thermodynamic and kinetic behavior and their potential properties for mobile hydrogen storage applications.
| Tipo de objeto: | Tesis (Tesis Doctoral en Ciencias de la Ingeniería) |
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| Palabras Clave: | Hydrides; Hidruros; Hydrogen; Hidrógeno; Storage; Almacenamiento; Milling; Fresado; Magnesium; Magnesio; Borohydrides; Borohidruros |
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| Materias: | Química > Química analítica Química > Ingeniería química Química > Materiales |
| Divisiones: | Aplicaciones de la energía nuclear > Tecnología de materiales y dispositivos > Fisicoquímica de materiales |
| Código ID: | 328 |
| Depositado Por: | Marisa G. Velazco Aldao |
| Depositado En: | 15 May 2012 14:35 |
| Última Modificación: | 15 May 2012 14:35 |
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