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- Genre: Academic theses
- Creators: Seo, Dong-Kyun
- Creators: Ayyanar, Raja
- Creators: Ranjan, Rajeev
- Creators: Yarger, Jeff
Description
This thesis focused on physicochemical and electrochemical projects directed towards two electrolyte types: 1) class of ionic liquids serving as electrolytes in the catholyte for alkali-metal ion conduction in batteries and 2) gel membrane for proton conduction in fuel cells; where overall aims were encouraged by the U.S. Department of Energy.
Large-scale, sodium-ion batteries are seen as global solutions to providing undisrupted electricity from sustainable, but power-fluctuating, energy production in the near future. Foreseen ideal advantages are lower cost without sacrifice of desired high-energy densities relative to present lithium-ion and lead-acid battery systems. Na/NiCl2 (ZEBRA) and Na/S battery chemistries, suffer from high operation temperature (>300ºC) and safety concerns following major fires consequent of fuel mixing after cell-separator rupturing. Initial interest was utilizing low-melting organic ionic liquid, [EMI+][AlCl4-], with well-known molten salt, NaAlCl4, to create a low-to-moderate operating temperature version of ZEBRA batteries; which have been subject of prior sodium battery research spanning decades. Isothermal conductivities of these electrolytes revealed a fundamental kinetic problem arisen from "alkali cation-trapping effect" yet relived by heat-ramping >140ºC.
Battery testing based on [EMI+][FeCl4-] with NaAlCl4 functioned exceptional (range 150-180ºC) at an impressive energy efficiency >96%. Newly prepared inorganic ionic liquid, [PBr4+][Al2Br7-]:NaAl2Br7, melted at 94ºC. NaAl2Br7 exhibited super-ionic conductivity 10-1.75 Scm-1 at 62ºC ensued by solid-state rotator phase transition. Also improved thermal stability when tested to 265ºC and less expensive chemical synthesis. [PBr4+][Al2Br7-] demonstrated remarkable, ionic decoupling in the liquid-state due to incomplete bromide-ion transfer depicted in NMR measurements.
Fuel cells are electrochemical devices generating electrical energy reacting hydrogen/oxygen gases producing water vapor. Principle advantage is high-energy efficiency of up to 70% in contrast to an internal combustion engine <40%. Nafion-based fuel cells are prone to carbon monoxide catalytic poisoning and polymer membrane degradation unless heavily hydrated under cell-pressurization. This novel "SiPOH" solid-electrolytic gel (originally liquid-state) operated in the fuel cell at 121oC yielding current and power densities high as 731mAcm-2 and 345mWcm-2, respectively. Enhanced proton conduction significantly increased H2 fuel efficiency to 89.7% utilizing only 3.1mlmin-1 under dry, unpressurized testing conditions. All these energy devices aforementioned evidently have future promise; therefore in early developmental stages.
Large-scale, sodium-ion batteries are seen as global solutions to providing undisrupted electricity from sustainable, but power-fluctuating, energy production in the near future. Foreseen ideal advantages are lower cost without sacrifice of desired high-energy densities relative to present lithium-ion and lead-acid battery systems. Na/NiCl2 (ZEBRA) and Na/S battery chemistries, suffer from high operation temperature (>300ºC) and safety concerns following major fires consequent of fuel mixing after cell-separator rupturing. Initial interest was utilizing low-melting organic ionic liquid, [EMI+][AlCl4-], with well-known molten salt, NaAlCl4, to create a low-to-moderate operating temperature version of ZEBRA batteries; which have been subject of prior sodium battery research spanning decades. Isothermal conductivities of these electrolytes revealed a fundamental kinetic problem arisen from "alkali cation-trapping effect" yet relived by heat-ramping >140ºC.
Battery testing based on [EMI+][FeCl4-] with NaAlCl4 functioned exceptional (range 150-180ºC) at an impressive energy efficiency >96%. Newly prepared inorganic ionic liquid, [PBr4+][Al2Br7-]:NaAl2Br7, melted at 94ºC. NaAl2Br7 exhibited super-ionic conductivity 10-1.75 Scm-1 at 62ºC ensued by solid-state rotator phase transition. Also improved thermal stability when tested to 265ºC and less expensive chemical synthesis. [PBr4+][Al2Br7-] demonstrated remarkable, ionic decoupling in the liquid-state due to incomplete bromide-ion transfer depicted in NMR measurements.
Fuel cells are electrochemical devices generating electrical energy reacting hydrogen/oxygen gases producing water vapor. Principle advantage is high-energy efficiency of up to 70% in contrast to an internal combustion engine <40%. Nafion-based fuel cells are prone to carbon monoxide catalytic poisoning and polymer membrane degradation unless heavily hydrated under cell-pressurization. This novel "SiPOH" solid-electrolytic gel (originally liquid-state) operated in the fuel cell at 121oC yielding current and power densities high as 731mAcm-2 and 345mWcm-2, respectively. Enhanced proton conduction significantly increased H2 fuel efficiency to 89.7% utilizing only 3.1mlmin-1 under dry, unpressurized testing conditions. All these energy devices aforementioned evidently have future promise; therefore in early developmental stages.
ContributorsTucker, Telpriore G (Author) / Angell, Charles A. (Committee member) / Moore, Ana (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2014
Description
Increasing concentrations of carbon dioxide in the atmosphere will inevitably lead to long-term changes in climate that can have serious consequences. Controlling anthropogenic emission of carbon dioxide into the atmosphere, however, represents a significant technological challenge. Various chemical approaches have been suggested, perhaps the most promising of these is based on electrochemical trapping of carbon dioxide using pyridine and derivatives. Optimization of this process requires a detailed understanding of the mechanisms of the reactions of reduced pyridines with carbon dioxide, which are not currently well known. This thesis describes a detailed mechanistic study of the nucleophilic and Bronsted basic properties of the radical anion of bipyridine as a model pyridine derivative, formed by one-electron reduction, with particular emphasis on the reactions with carbon dioxide. A time-resolved spectroscopic method was used to characterize the key intermediates and determine the kinetics of the reactions of the radical anion and its protonated radical form. Using a pulsed nanosecond laser, the bipyridine radical anion could be generated in-situ in less than 100 ns, which allows fast reactions to be monitored in real time. The bipyridine radical anion was found to be a very powerful one-electron donor, Bronsted base and nucleophile. It reacts by addition to the C=O bonds of ketones with a bimolecular rate constant around 1* 107 M-1 s-1. These are among the fastest nucleophilic additions that have been reported in literature. Temperature dependence studies demonstrate very low activation energies and large Arrhenius pre-exponential parameters, consistent with very high reactivity. The kinetics of E2 elimination, where the radical anion acts as a base, and SN2 substitution, where the radical anion acts as a nucleophile, are also characterized by large bimolecular rate constants in the range ca. 106 - 107 M-1 s-1. The pKa of the bipyridine radical anion was measured using a kinetic method and analysis of the data using a Marcus theory model for proton transfer. The bipyridine radical anion is found to have a pKa of 40±5 in DMSO. The reorganization energy for the proton transfer reaction was found to be 70±5 kJ/mol. The bipyridine radical anion was found to react very rapidly with carbon dioxide, with a bimolecular rate constant of 1* 108 M-1 s-1 and a small activation energy, whereas the protonated radical reacted with carbon dioxide with a rate constant that was too small to measure. The kinetic and thermodynamic data obtained in this work can be used to understand the mechanisms of the reactions of pyridines with carbon dioxide under reducing conditions.
ContributorsRanjan, Rajeev (Author) / Gould, Ian R (Thesis advisor) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeff (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2015
Description
Our daily life is becoming more and more reliant on services provided by the infrastructures
power, gas , communication networks. Ensuring the security of these
infrastructures is of utmost importance. This task becomes ever more challenging as
the inter-dependence among these infrastructures grows and a security breach in one
infrastructure can spill over to the others. The implication is that the security practices/
analysis recommended for these infrastructures should be done in coordination.
This thesis, focusing on the power grid, explores strategies to secure the system that
look into the coupling of the power grid to the cyber infrastructure, used to manage
and control it, and to the gas grid, that supplies an increasing amount of reserves to
overcome contingencies.
The first part (Part I) of the thesis, including chapters 2 through 4, focuses on
the coupling of the power and the cyber infrastructure that is used for its control and
operations. The goal is to detect malicious attacks gaining information about the
operation of the power grid to later attack the system. In chapter 2, we propose a
hierarchical architecture that correlates the analysis of high resolution Micro-Phasor
Measurement Unit (microPMU) data and traffic analysis on the Supervisory Control
and Data Acquisition (SCADA) packets, to infer the security status of the grid and
detect the presence of possible intruders. An essential part of this architecture is
tied to the analysis on the microPMU data. In chapter 3 we establish a set of anomaly
detection rules on microPMU data that
flag "abnormal behavior". A placement strategy
of microPMU sensors is also proposed to maximize the sensitivity in detecting anomalies.
In chapter 4, we focus on developing rules that can localize the source of an events
using microPMU to further check whether a cyber attack is causing the anomaly, by
correlating SCADA traffic with the microPMU data analysis results. The thread that
unies the data analysis in this chapter is the fact that decision are made without fully estimating the state of the system; on the contrary, decisions are made using
a set of physical measurements that falls short by orders of magnitude to meet the
needs for observability. More specifically, in the first part of this chapter (sections 4.1-
4.2), using microPMU data in the substation, methodologies for online identification of
the source Thevenin parameters are presented. This methodology is used to identify
reconnaissance activity on the normally-open switches in the substation, initiated
by attackers to gauge its controllability over the cyber network. The applications
of this methodology in monitoring the voltage stability of the grid is also discussed.
In the second part of this chapter (sections 4.3-4.5), we investigate the localization
of faults. Since the number of PMU sensors available to carry out the inference
is insufficient to ensure observability, the problem can be viewed as that of under-sampling
a "graph signal"; the analysis leads to a PMU placement strategy that can
achieve the highest resolution in localizing the fault, for a given number of sensors.
In both cases, the results of the analysis are leveraged in the detection of cyber-physical
attacks, where microPMU data and relevant SCADA network traffic information
are compared to determine if a network breach has affected the integrity of the system
information and/or operations.
In second part of this thesis (Part II), the security analysis considers the adequacy
and reliability of schedules for the gas and power network. The motivation for
scheduling jointly supply in gas and power networks is motivated by the increasing
reliance of power grids on natural gas generators (and, indirectly, on gas pipelines)
as providing critical reserves. Chapter 5 focuses on unveiling the challenges and
providing solution to this problem.
power, gas , communication networks. Ensuring the security of these
infrastructures is of utmost importance. This task becomes ever more challenging as
the inter-dependence among these infrastructures grows and a security breach in one
infrastructure can spill over to the others. The implication is that the security practices/
analysis recommended for these infrastructures should be done in coordination.
This thesis, focusing on the power grid, explores strategies to secure the system that
look into the coupling of the power grid to the cyber infrastructure, used to manage
and control it, and to the gas grid, that supplies an increasing amount of reserves to
overcome contingencies.
The first part (Part I) of the thesis, including chapters 2 through 4, focuses on
the coupling of the power and the cyber infrastructure that is used for its control and
operations. The goal is to detect malicious attacks gaining information about the
operation of the power grid to later attack the system. In chapter 2, we propose a
hierarchical architecture that correlates the analysis of high resolution Micro-Phasor
Measurement Unit (microPMU) data and traffic analysis on the Supervisory Control
and Data Acquisition (SCADA) packets, to infer the security status of the grid and
detect the presence of possible intruders. An essential part of this architecture is
tied to the analysis on the microPMU data. In chapter 3 we establish a set of anomaly
detection rules on microPMU data that
flag "abnormal behavior". A placement strategy
of microPMU sensors is also proposed to maximize the sensitivity in detecting anomalies.
In chapter 4, we focus on developing rules that can localize the source of an events
using microPMU to further check whether a cyber attack is causing the anomaly, by
correlating SCADA traffic with the microPMU data analysis results. The thread that
unies the data analysis in this chapter is the fact that decision are made without fully estimating the state of the system; on the contrary, decisions are made using
a set of physical measurements that falls short by orders of magnitude to meet the
needs for observability. More specifically, in the first part of this chapter (sections 4.1-
4.2), using microPMU data in the substation, methodologies for online identification of
the source Thevenin parameters are presented. This methodology is used to identify
reconnaissance activity on the normally-open switches in the substation, initiated
by attackers to gauge its controllability over the cyber network. The applications
of this methodology in monitoring the voltage stability of the grid is also discussed.
In the second part of this chapter (sections 4.3-4.5), we investigate the localization
of faults. Since the number of PMU sensors available to carry out the inference
is insufficient to ensure observability, the problem can be viewed as that of under-sampling
a "graph signal"; the analysis leads to a PMU placement strategy that can
achieve the highest resolution in localizing the fault, for a given number of sensors.
In both cases, the results of the analysis are leveraged in the detection of cyber-physical
attacks, where microPMU data and relevant SCADA network traffic information
are compared to determine if a network breach has affected the integrity of the system
information and/or operations.
In second part of this thesis (Part II), the security analysis considers the adequacy
and reliability of schedules for the gas and power network. The motivation for
scheduling jointly supply in gas and power networks is motivated by the increasing
reliance of power grids on natural gas generators (and, indirectly, on gas pipelines)
as providing critical reserves. Chapter 5 focuses on unveiling the challenges and
providing solution to this problem.
ContributorsJamei, Mahdi (Author) / Scaglioe, Anna (Thesis advisor) / Ayyanar, Raja (Committee member) / Hedman, Kory W (Committee member) / Kosut, Oliver (Committee member) / Arizona State University (Publisher)
Created2018