ASU Electronic Theses and Dissertations
This collection includes most of the ASU Theses and Dissertations from 2011 to present. ASU Theses and Dissertations are available in downloadable PDF format; however, a small percentage of items are under embargo. Information about the dissertations/theses includes degree information, committee members, an abstract, supporting data or media.
In addition to the electronic theses found in the ASU Digital Repository, ASU Theses and Dissertations can be found in the ASU Library Catalog.
Dissertations and Theses granted by Arizona State University are archived and made available through a joint effort of the ASU Graduate College and the ASU Libraries. For more information or questions about this collection contact or visit the Digital Repository ETD Library Guide or contact the ASU Graduate College at gradformat@asu.edu.
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- All Subjects: Alternative Energy
- Creators: Crozier, Peter
Description
Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates.
ContributorsRaghavan, Rahul (Author) / Chan, Candace K. (Thesis advisor) / Crozier, Peter (Committee member) / Petuskey, William T (Committee member) / Arizona State University (Publisher)
Created2013
Description
Photocatalytic water splitting over suspended nanoparticles represents a potential solution for achieving CO2-neutral energy generation and storage. To design efficient photocatalysts, a fundamental understanding of the material’s structure, electronic properties, defects, and how these are controlled via synthesis is essential. Both bulk and nanoscale materials characterization, in addition to various performance metrics, can be combined to elucidate functionality at multiple length scales. In this work, two promising visible light harvesting systems are studied in detail: Pt-functionalized graphitic carbon nitrides (g-CNxHys) and TiO2-supported CeO2-x composites.
Electron energy-loss spectroscopy (EELS) is used to sense variations in the local concentration of amine moieties (defects believed to facilitate interfacial charge transfer) at the surface of a g-CNxHy flake. Using an aloof-beam configuration, spatial resolution is maximized while minimizing damage thus providing nanoscale vibrational fingerprints similar to infrared absorption spectra. Structural disorder in g-CNxHys is further studied using transmission electron microscopy at low electron fluence rates. In-plane structural fluctuations revealed variations in the local azimuthal orientation of the heptazine building blocks, allowing planar domain sizes to be related to the average polymer chain length. Furthermore, competing factors regulating photocatalytic performance in a series of Pt/g-CNxHys is elucidated. Increased polymer condensation in the g-CNxHy support enhances the rate of charge transfer to reactants owing to higher electronic mobility. However, active site densities are over 3x lower on the most condensed g-CNxHy which ultimately limits its H2 evolution rate (HER). Based on these findings, strategies to improve the cocatalyst configuration on intrinsically active supports are given.
In TiO2/CeO2-x photocatalysts, the effect of the support particle size on the bulk
anoscale properties and photocatalytic performance is investigated. Small anatase supports facilitate highly dispersed CeO2-x species, leading to increased visible light absorption and HERs resulting from a higher density of mixed metal oxide (MMO) interfaces with Ce3+ species. Using monochromated EELS, bandgap states associated with MMO interfaces are detected, revealing electronic transitions from 0.5 eV up to the bulk bandgap onset of anatase. Overall, the electron microscopy/spectroscopy techniques developed and applied herein sheds light onto the relevant defects and limiting processes operating within these photocatalyst systems thus suggesting rational design strategies.
Electron energy-loss spectroscopy (EELS) is used to sense variations in the local concentration of amine moieties (defects believed to facilitate interfacial charge transfer) at the surface of a g-CNxHy flake. Using an aloof-beam configuration, spatial resolution is maximized while minimizing damage thus providing nanoscale vibrational fingerprints similar to infrared absorption spectra. Structural disorder in g-CNxHys is further studied using transmission electron microscopy at low electron fluence rates. In-plane structural fluctuations revealed variations in the local azimuthal orientation of the heptazine building blocks, allowing planar domain sizes to be related to the average polymer chain length. Furthermore, competing factors regulating photocatalytic performance in a series of Pt/g-CNxHys is elucidated. Increased polymer condensation in the g-CNxHy support enhances the rate of charge transfer to reactants owing to higher electronic mobility. However, active site densities are over 3x lower on the most condensed g-CNxHy which ultimately limits its H2 evolution rate (HER). Based on these findings, strategies to improve the cocatalyst configuration on intrinsically active supports are given.
In TiO2/CeO2-x photocatalysts, the effect of the support particle size on the bulk
anoscale properties and photocatalytic performance is investigated. Small anatase supports facilitate highly dispersed CeO2-x species, leading to increased visible light absorption and HERs resulting from a higher density of mixed metal oxide (MMO) interfaces with Ce3+ species. Using monochromated EELS, bandgap states associated with MMO interfaces are detected, revealing electronic transitions from 0.5 eV up to the bulk bandgap onset of anatase. Overall, the electron microscopy/spectroscopy techniques developed and applied herein sheds light onto the relevant defects and limiting processes operating within these photocatalyst systems thus suggesting rational design strategies.
ContributorsHaiber, Diane Michelle (Author) / Crozier, Peter (Thesis advisor) / Chan, Candace (Committee member) / Liu, Jingyue (Committee member) / Treacy, Michael (Committee member) / Arizona State University (Publisher)
Created2019