Structural Characterization of Metal Hydrides for Energy Applications

Hydrogen can be an unlimited source of clean energy for future because of its very high energy density compared to the conventional fuels like gasoline. An efficient and safer way of storing hydrogen is in metals and alloys as hydrides. Light metal hydrides, alanates and borohydrides have very good hydrogen storage capacity, but high operation temperatures hinder their application. Improvement of thermodynamic properties of these hydrides is important for their commercial use as a source of energy. Application of pressure on materials can have influence on their properties favoring hydrogen storage. Hydrogen desorption in many complex hydrides occurs above the transition temperature. Therefore, it is important to study the physical properties of the hydride compounds at ambient and high pressure and/or high temperature conditions, which can assist in the design of suitable storage materials with desired thermodynamic properties. ^ The high pressure-temperature phase diagram, thermal expansion and compressibility have only been evaluated for a limited number of hydrides so far. This situation serves as a main motivation for studying such properties of a number of technologically important hydrides. Focus of this dissertation was on X-ray diffraction and Raman spectroscopy studies of Mg2FeH6, Ca(BH4) 2, Mg(BH4)2, NaBH4, NaAlH4, LiAlH4, LiNH2BH3 and mixture of MgH 2 with AlH3 or Si, at different conditions of pressure and temperature, to obtain their bulk modulus and thermal expansion coefficient. These data are potential source of information regarding inter-atomic forces and also serve as a basis for developing theoretical models. Some high pressure phases were identified for the complex hydrides in this study which may have better hydrogen storage properties than the ambient phase. The results showed that the highly compressible B-H or Al-H bonds and the associated bond disordering under pressure is responsible for phase transitions observed in brorohydrides or alanates. Complex hydrides exhibited very high compressibility suggesting possibility to destabilize them with pressure. With high capacity and favorable thermodynamics, complex hydrides are suitable for reversible storage. Further studies are required to overcome the kinetic barriers in complex hydrides by catalytic addition. A comparative study of the hydride properties with that of the constituting metal, and their inter relationships were carried out with many interesting features.^

Improving Storage with Stackable Extensions

Storage is a central part of computing. Driven by exponentially increasing content generation rate and a widening performance gap between memory and secondary storage, researchers are in the perennial quest to push for further innovation. This has resulted in novel ways to "squeeze" more capacity and performance out of current and emerging storage technology. Adding intelligence and leveraging new types of storage devices has opened the door to a whole new class of optimizations to save cost, improve performance, and reduce energy consumption. In this dissertation, we first develop, analyze, and evaluate three storage extensions. Our first extension tracks application access patterns and writes data in the way individual applications most commonly access it to benefit from the sequential throughput of disks. Our second extension uses a lower power flash device as a cache to save energy and turn off the disk during idle periods. Our third extension is designed to leverage the characteristics of both disks and solid state devices by placing data in the most appropriate device to improve performance and save power. In developing these systems, we learned that extending the storage stack is a complex process. Implementing new ideas incurs a prolonged and cumbersome development process and requires developers to have advanced knowledge of the entire system to ensure that extensions accomplish their goal without compromising data recoverability. Futhermore, storage administrators are often reluctant to deploy specific storage extensions without understanding how they interact with other extensions and if the extension ultimately achieves the intended goal. We address these challenges by using a combination of approaches. First, we simplify the storage extension development process with system-level infrastructure that implements core functionality commonly needed for storage extension development. Second, we develop a formal theory to assist administrators deploy storage extensions while guaranteeing that the given high level goals are satisfied. There are, however, some cases for which our theory is inconclusive. For such scenarios we present an experimental methodology that allows administrators to pick an extension that performs best for a given workload. Our evaluation demostrates the benefits of both the infrastructure and the formal theory.

Enhanced 3-dimensional carbon nanotube based anodes for lithium-ion battery applications

A prototype 3-dimensional (3D) anode, based on multiwall carbon nanotubes (MWCNTs), for Li-ion batteries (LIBs), with potential use in Electric Vehicles (EVs) was investigated. The unique 3D design of the anode allowed much higher areal mass density of MWCNTs as active materials, resulting in more amount of Li+ ion intake, compared to that of a conventional 2D counterpart. Furthermore, 3D amorphous Si/MWCNTs hybrid structure offered enhancement in electrochemical response (specific capacity 549 mAhg–1 ). Also, an anode stack was fabricated to further increase the areal or volumetric mass density of MWCNTs. An areal mass density of the anode stack 34.9 mg/cm2 was attained, which is 1,342% higher than the value for a single layer 2.6 mg/cm2. Furthermore, the binder-assisted and hot-pressed anode stack yielded the average reversible, stable gravimetric and volumetric specific capacities of 213 mAhg–1 and 265 mAh/cm3, respectively (at 0.5C). Moreover, a large-scale patterned novel flexible 3D MWCNTs-graphene-polyethylene terephthalate (PET) anode structure was prepared. It generated a reversible specific capacity of 153 mAhg–1 at 0.17C and cycling stability of 130 mAhg –1 up to 50 cycles at 1.7C.