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Preparación, estudio y optimización de amiduros de litio y magnesio para almacenamiento de hidrógeno / Preparation, study and optimization of lithium and magnesium amidides for hydrogen storage

Amica, Guillermina (2018) Preparación, estudio y optimización de amiduros de litio y magnesio para almacenamiento de hidrógeno / Preparation, study and optimization of lithium and magnesium amidides for hydrogen storage. Tesis Doctoral en Ciencias de la Ingeniería, Universidad Nacional de Cuyo, Instituto Balseiro.

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Resumen en español

El desarrollo de esta Tesis de Doctorado en Ciencias de la Ingeniería se centró en el estudio de materiales compuestos para almacenamiento de hidrógeno basado en amiduros, tanto de litio como de magnesio, con propiedades optimizadas para su empleo eficiente en aplicaciones móviles. En una primera parte, se estudió el sistema Li-N-H y se introdujeron mejoras en el proceso de síntesis del material LiNH_2-LiH. Se analizó sistemáticamente el efecto del agregado de diferentes hidruros (MgH_2, CaH_2 y TiH_2) sobre la cinética y la estabilidad luego de numerosos ciclos de absorción/desorción de hidrógeno. Para cada sistema, se presentó una propuesta de camino de reacción y pudo afirmarse que la deshidrogenación del material LiNH_2-1,6LiH, con y sin aditivos, presenta un control difusivo. Si bien se demostró la potencialidad del sistema Li-N-H como almacenador de hidrógeno, se concluyó que la principal limitación es su alta temperatura de operación. La demostración de la modificación favorable de la termodinámica del sistema Li-N-H con la incorporación de Mg, sugirió la importancia del análisis de sistemas pseudo-cuaternarios, conteniendo Li y Mg. En una segunda parte, en la exploración del sistema Li-Mg-N-H, se estudió el material compuesto Mg(NH_2)_2-2LiH y se investigó el efecto de la presencia de un conductor iónico rápido de litio (Li_4(NH_2)_3BH_4) en su deshidrogenación. El rol catalítico de esta fase permitió justificar las grandes mejoras observadas en las velocidades de deshidrogenación y rehidrogenación del material. Si bien no fue posible garantizar la desestabilización termodinámica por la dificultad en alcanzar condiciones de medición en el equilibrio, el estudio de sucesivas isotermas de presión–composición junto con la caracterización estructural de los materiales en diferentes etapas del proceso de deshidrogenación, permitió la reconstrucción de las vías de reacción, demostrando la participación activa de la fase Li_4(NH_2)_3BH_4 en diferentes reacciones. Sobre las mediciones de deshidrogenación de este material compuesto, se analizaron los procesos limitantes de la velocidad de reacción. A partir de la combinación de dos modelos cinéticos, un mecanismo de nucleación y crecimiento que ajusta los valores experimentales a bajas conversiones y un modelo difusivo tridimensional, a altas, se presentaron las ecuaciones que describen la velocidad de desorción del sistema en función del grado de avance de la reacción y de la presión. Adicionalmente, se mostraron estudios relacionados con la desestabilización de la fase Li_4(NH_2)_3BH_4 mediante el dopaje con LiH y el uso de catalizadores a base de Co y Ni. Finalmente, se analizaron las perspectivas económicas relacionadas con la factibilidad del empleo del hidrógeno como vector energético en una aplicación móvil, considerando el costo del hidrógeno, el del tanque almacenador y el de la matriz sólida optimizada estudiada en el Capítulo 4 de esta Tesis. Además se realizó una comparación con las tecnologías que utilizan hidrógeno almacenado a alta presión. En síntesis, la presente Tesis proporciona estudios sobre matrices sólidas almacenadoras de hidrógeno de los sistemas Li-N-H y Li-Mg-N-H, aportando conocimiento no solo acerca de sus características microestructurales y estructurales, sino también del entendimiento de su termodinámica y cinética de la interacción con hidrógeno. Al tratarse de sistemas que pueden almacenar una cantidad suficiente de hidrógeno con propiedades termodinámicas y cinéticas prometedoras respecto a las otras clases de materiales complejos, resultan muy atractivos para ser utilizados en aplicaciones a bordo en vehículos con celdas de combustible. La necesidad global de diversificar la matriz energética le confiere al H_2 un rol fundamental como vector energético capaz de crear una economía alternativa a la actual basada en combustibles fósiles.

Resumen en inglés

The development of this PhD Thesis in Engineering Sciences has been focused on the study of composites for hydrogen storage, based on lithium and magnesium amides, with optimized properties for its efficient use in mobile applications. In the first part of the Thesis, the Li-N-H system was studied and improvements in the LiNH_2-LiH synthesis process were introduced. The effect of the different hydrides (MgH_2, CaH_2 and TiH_2) on the kinetics and stability after numerous cycles of absorption / desorption of hydrogen was systematically analyzed. For each system a proposal for a reaction path was presented and it could be affirmed that the dehydrogenation of the LiNH_2-1.6LiH material, with and without additives, presents a diffusive control. Although the potentiality of the Li-N-H system was demonstrated, it was concluded that the main limitation is its high operating temperature. The enhancement of its thermodynamic properties by the incorporation of Mg, suggested the importance of the analysis of pseudo-quaternary systems, containing Li and Mg. In a second part, in the exploration of the Li-Mg-NH system, the Mg(NH_2)_2- 2LiH composite was studied and the effect of the presence of a fast ionic lithium conductor (Li_4(NH_2)_3BH_4) was investigated. The catalytic role of this phase allowed to justify the great improvements observed in the dehydrogenation and rehydrogenation rates. Although it was not possible to guarantee thermodynamic destabilization due to the difficulty in achieving equilibrium measurement conditions, the study of successive pressure-composition isotherms together with the structural characterization of the materials at different stages of the dehydrogenation process, allowed the reconstruction of the reaction pathways, demonstrating the active participation of the Li_4(NH_2)3BH_4 phase in different reactions. Analyzing the dehydrogenation measurements of this material, the limiting processes of the reaction rate were determined. By combining two kinetic models, a mechanism of nucleation and growth and a 3D diffusive model, the equations that describe the desorption rates of the system according to conversion and hydrogen back pressure were obtained. Additionally, studies related to the destabilization of the Li_4(NH_2)_3BH_4 phase trough doping with LiH and Co / Ni- based catalysts were presented. Finally, an economic analysis was carried out to evaluate the feasibility of using the optimized solid matrix as material for hydrogen storage. The costs of hydrogen production trough different processes, the storage tank and the hydride material were considered. In addition, a comparison with other storage alternatives was included. In summary, this Thesis presents studies on solid hydrogen storage matrices of the Li-N-H and Li-Mg-N-H systems, providing knowledge not only about their microstructural characteristics, but also about the understanding of their thermodynamics and kinetics of interaction with hydrogen. As they are systems that can store a sufficient amount of hydrogen with promising thermodynamic and kinetic properties compared to other complex materials, they are attractive to be employed in on-board applications in vehicles with fuel cells. The global need to diversify the energy matrix confers H_2 a fundamental role as an energy vector capable of creating an alternative economy to the current one based on fossil fuels.

Tipo de objeto:	Tesis (Tesis Doctoral en Ciencias de la Ingeniería)
Palabras Clave:	Hydrogen; Hidrógeno; Energy; Energía; Storage; Almacenamiento; Lithuim; Litio; Materials; Materiales, Amides, Amidas.
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Materias:	Ingeniería > Almacenamiento de hidrógeno
Divisiones:	Aplicaciones de la energía nuclear > Tecnología de materiales y dispositivos > Fisicoquímica de materiales
Código ID:	729
Depositado Por:	Tamara Cárcamo
Depositado En:	18 Dic 2018 14:01
Última Modificación:	18 Dic 2018 14:01

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