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: Ghirlanda, Giovanna
- Creators: Kannan, Arunachala Mada
Performance evaluation and characterization of lithium-ion cells under simulated PHEVs' drive cycles
Description
Increasing demand for reducing the stress on fossil fuels has motivated automotive industries to shift towards sustainable modes of transport through electric and hybrid electric vehicles. Most fuel efficient cars of year 2016 are hybrid vehicles as reported by environmental protection agency. Hybrid vehicles operate with internal combustion engine and electric motors powered by batteries, and can significantly improve fuel economy due to downsizing of the engine. Whereas, Plug-in hybrids (PHEVs) have an additional feature compared to hybrid vehicles i.e. recharging batteries through external power outlets. Among hybrid powertrains, lithium-ion batteries have emerged as a major electrochemical storage source for propulsion of vehicles.
In PHEVs, batteries operate under charge sustaining and charge depleting mode based on torque requirement and state of charge. In the current article, 26650 lithium-ion cells were cycled extensively at 25 and 50 oC under charge sustaining mode to monitor capacity and cell impedance values followed by analyzing the Lithium iron phosphate (LiFePO4) cathode material by X-ray diffraction analysis (XRD). High frequency resistance measured by electrochemical impedance spectroscopy was found to increase significantly under high temperature cycling, leading to power fading. No phase change in LiFePO4 cathode material is observed after 330 cycles at elevated temperature under charge sustaining mode from the XRD analysis. However, there was significant change in crystallite size of the cathode active material after charge/discharge cycling with charge sustaining mode. Additionally, 18650 lithium-ion cells were tested under charge depleting mode to monitor capacity values.
In PHEVs, batteries operate under charge sustaining and charge depleting mode based on torque requirement and state of charge. In the current article, 26650 lithium-ion cells were cycled extensively at 25 and 50 oC under charge sustaining mode to monitor capacity and cell impedance values followed by analyzing the Lithium iron phosphate (LiFePO4) cathode material by X-ray diffraction analysis (XRD). High frequency resistance measured by electrochemical impedance spectroscopy was found to increase significantly under high temperature cycling, leading to power fading. No phase change in LiFePO4 cathode material is observed after 330 cycles at elevated temperature under charge sustaining mode from the XRD analysis. However, there was significant change in crystallite size of the cathode active material after charge/discharge cycling with charge sustaining mode. Additionally, 18650 lithium-ion cells were tested under charge depleting mode to monitor capacity values.
ContributorsBadami, Pavan Pramod (Author) / Kannan, Arunachala Mada (Thesis advisor) / Huang, Huei Ping (Thesis advisor) / Ren, Yi (Committee member) / Arizona State University (Publisher)
Created2016
Description
The utilization of solar energy requires an efficient means of its storage as fuel. In bio-inspired artificial photosynthesis, light energy can be used to drive water oxidation, but catalysts that produce molecular oxygen from water are required. This dissertation demonstrates a novel complex utilizing earth-abundant Ni in combination with glycine as an efficient catalyst with a modest overpotential of 0.475 ± 0.005 V for a current density of 1 mA/cm2 at pH 11. The production of molecular oxygen at a high potential was verified by measurement of the change in oxygen concentration, yielding a Faradaic efficiency of 60 ± 5%. This Ni species can achieve a current density of 4 mA/cm2 that persists for at least 10 hours. Based upon the observed pH dependence of the current amplitude and oxidation/reduction peaks, the catalysis is an electron-proton coupled process. In addition, to investigate the binding of divalent metals to proteins, four peptides were designed and synthesized with carboxylate and histidine ligands. The binding of the metals was characterized by monitoring the metal-induced changes in circular dichroism spectra. Cyclic voltammetry demonstrated that bound copper underwent a Cu(I)/Cu(II) oxidation/reduction change at a potential of approximately 0.32 V in a quasi-reversible process. The relative binding affinity of Mn(II), Fe(II), Co(II), Ni(II) and Cu(II) to the peptides is correlated with the stability constants of the Irving-Williams series for divalent metal ions. A potential application of these complexes of transition metals with amino acids or peptides is in the development of artificial photosynthetic cells.
ContributorsWang, Dong (Author) / Allen, James P. (Thesis advisor) / Ghirlanda, Giovanna (Committee member) / Redding, Kevin (Committee member) / Arizona State University (Publisher)
Created2014
Description
As sunlight is an ideal source of energy on a global scale, there are several approaches being developed to harvest it and convert it to a form that can be used. One of these is though mimicking the processes in natural photosynthesis. Artificial photosynthetic systems include dye sensitized solar cells for the conversion of sunlight to electricity, and photoelectrosynthetic cells which use sunlight to drive water oxidation and hydrogen production to convert sunlight to energy stored in fuel. Both of these approaches include the process of the conversion of light energy into chemical potential in the form of a charge-separated state via molecular compounds. Porphyrins are commonly used as sensitizers as they have well suited properties for these applications. A high potential porphyrin with four nitrile groups at the beta positions, a β-cyanoporphyrin (CyP), was investigated and found to be an excellent electron acceptor, as well as have the necessary properties to be used as a sensitizer for photoelectrosynthetic cells for water oxidation. A new synthetic method was developed which allowed for the CyP to be used in a number of studies in artificial photosynthetic systems. This dissertation reports the theories behind, and the results of four studies utilizing a CyP for the first time; as a sensitizer in a DSSC for an investigation of its use in light driven water oxidation photoelectrosynthetic cells, as an electron acceptor in a proton coupled electron transfer system, in a carotene-CyP dyad to study energy and electron transfer processes between these moieties, and in a molecular triad to study a unique electron transfer process from a C60 radical anion to the CyP. It has been found that CyPs can be used as powerful electron acceptors in molecular systems to provide a large driving force for electron transfer that can aid in the process of the conversion of light to electrochemical potential. The results from these studies have led to a better understanding of the properties of CyPs, and have provided new insight into several electron transfer reactions.
ContributorsAntoniuk-Pablant, Antaeres' Dawn (Author) / Gust, Devens (Thesis advisor) / Moore, Ana L (Committee member) / Ghirlanda, Giovanna (Committee member) / Arizona State University (Publisher)
Created2015
Description
The automotive industry is committed to moving towards sustainable modes of transportation through electrified vehicles to improve the fuel economy with a reduced carbon footprint. In this context, battery-operated hybrid, plug-in hybrid and all-electric vehicles (EVs) are becoming commercially viable throughout the world. Lithium-ion (Li-ion) batteries with various active materials, electrolytes, and separators are currently being used for electric vehicle applications. Specifically, lithium-ion batteries with Lithium Iron Phosphate (LiFePO4 - LFP) and Lithium Nickel Manganese Cobalt Oxide (Li(NiMnCo)O2 - NMC) cathodes are being studied mainly due to higher cycle life and higher energy density values, respectively. In the present work, 26650 Li-ion batteries with LFP and NMC cathodes were evaluated for Plug-in Hybrid Electric Vehicle (PHEV) applications, using the Federal Urban Driving Schedule (FUDS) to discharge the batteries with 20 A current in simulated Arizona, USA weather conditions (50 ⁰C & <10% RH). In addition, 18650 lithium-ion batteries (LFP cathode material) were evaluated under PHEV mode with 30 A current to accelerate the ageing process, and to monitor the capacity values and material degradation. To offset the high initial cost of the batteries used in electric vehicles, second-use of these retired batteries is gaining importance, and the possibility of second-life use of these tested batteries was also examined under constant current charge/discharge cycling at 50 ⁰C.
The capacity degradation rate under the PHEV test protocol for batteries with NMC-based cathode (16% over 800 cycles) was twice the degradation compared to batteries with LFP-based cathode (8% over 800 cycles), reiterating the fact that batteries with LFP cathodes have a higher cycle life compared to other lithium battery chemistries. Also, the high frequency resistance measured by electrochemical impedance spectroscopy (EIS) was found to increase significantly with cycling, leading to power fading for both the NMC- as well as LFP-based batteries. The active materials analyzed using X-ray diffraction (XRD) showed no significant phase change in the materials after 800 PHEV cycles. For second-life tests, these batteries were subjected to a constant charge-discharge cycling procedure to analyze the capacity degradation and materials characteristics.
The capacity degradation rate under the PHEV test protocol for batteries with NMC-based cathode (16% over 800 cycles) was twice the degradation compared to batteries with LFP-based cathode (8% over 800 cycles), reiterating the fact that batteries with LFP cathodes have a higher cycle life compared to other lithium battery chemistries. Also, the high frequency resistance measured by electrochemical impedance spectroscopy (EIS) was found to increase significantly with cycling, leading to power fading for both the NMC- as well as LFP-based batteries. The active materials analyzed using X-ray diffraction (XRD) showed no significant phase change in the materials after 800 PHEV cycles. For second-life tests, these batteries were subjected to a constant charge-discharge cycling procedure to analyze the capacity degradation and materials characteristics.
ContributorsVaidya, Rutvik Milind (Author) / Kannan, Arunachala Mada (Thesis advisor) / Alford, Terry (Committee member) / Wishart, Jeffrey (Committee member) / Arizona State University (Publisher)
Created2017