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This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached.
ContributorsAnsari, Younes (Author) / Angell, Charles A (Thesis advisor) / Richert, Ranko (Committee member) / Chizmeshya, Andrew (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
Description
Proton exchange membrane fuel cells have attracted immense research activities from the inception of the technology due to its high stability and performance capabilities. The major obstacle from commercialization is the cost of the catalyst material in manufacturing the fuel cell. In the present study, the major focus in PEMFCs has been in reduction of the cost of the catalyst material using graphene, thin film coated and Organometallic Molecular catalysts. The present research is focused on improving the durability and active surface area of the catalyst materials with low platinum loading using nanomaterials to reduce the effective cost of the fuel cells. Performance, Electrochemical impedance spectroscopy, oxygen reduction and surface morphology studies were performed on each manufactured material.
Alkaline fuel cells with anion exchange membrane get immense attention due to very attractive opportunity of using non-noble metal catalyst materials. In the present study, cathodes with various organometallic cathode materials were prepared and investigated for alkaline membrane fuel cells for oxygen reduction and performance studies. Co and Fe Phthalocyanine catalyst materials were deposited on multi-walled carbon nanotubes (MWCNTs) support materials. Membrane Electrode Assemblies (MEAs) were fabricated using Tokuyama Membrane (#A901) with cathodes containing Co and Fe Phthalocyanine/MWCNTs and Pt/C anodes. Fuel cell performance of the MEAs was examined.
Alkaline fuel cells with anion exchange membrane get immense attention due to very attractive opportunity of using non-noble metal catalyst materials. In the present study, cathodes with various organometallic cathode materials were prepared and investigated for alkaline membrane fuel cells for oxygen reduction and performance studies. Co and Fe Phthalocyanine catalyst materials were deposited on multi-walled carbon nanotubes (MWCNTs) support materials. Membrane Electrode Assemblies (MEAs) were fabricated using Tokuyama Membrane (#A901) with cathodes containing Co and Fe Phthalocyanine/MWCNTs and Pt/C anodes. Fuel cell performance of the MEAs was examined.
ContributorsKolli, Sri Harsha (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Nam, Changho (Committee member) / Peng, Xihong (Committee member) / Arizona State University (Publisher)
Created2014
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
Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2*-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set of experiments in C4dMImTf solicited water as the proton donor for oxygen reduction in an approximation of the aqueous alkaline case. The water content was varied between extremely dry (<0.1 mol% H2O) and saturated (approximately 15.8 mol% H2O}). As the water content increased so too did the extent of oxygen reduction eventually approach two electrons on both Pt and GC. However, additional water led to a linear increase in the Tafel slope under enhanced mass transport conditions up to the point of 10 mol% water. This inhibition of oxygen adsorption is the result of the interaction between superoxide and water and more specifically is proposed to be associated with decomposition of theC4dMIm+ cation by hydroxide at the elevated temperatures required for the experiment. Oxygen reduction on both Pt and GC follows Nernstian behavior as the water content is increased. Separate mechanisms for oxygen reduction on Pt and GC are proposed based on the nature of the Nernstian response in these systems.
ContributorsZeller, Robert August (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2011
Description
This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project explores the evolution of bulk stress that occurs during intercalation (extraction) of lithium (Li) and formation of a solid electrolyte interphase during electrochemical reduction (oxidation) of Li at graphitic electrodes. Electrocapillarity measurements have shown that hydrogen and hydroxide adsorption are compressive on Pt{111}, Ru/Pt{111}, and Ru{0001}. The adsorption-induced surface stresses correlate strongly with adsorption charge. Electrocatalytic oxidation of CO on Pt{111} and Ru/Pt{111} gives a tensile surface stress. A numerical method was developed to separate both current and stress into background and active components. Applying this model to the CO oxidation signal on Ru{0001} gives a tensile surface stress and elucidates the rate limiting steps on all three electrodes. The enhanced catalysis of Ru/Pt{111} is confirmed to be bi-functional in nature: Ru provides adsorbed hydroxide to Pt allowing for rapid CO oxidation. The majority of Li-ion batteries have anodes consisting of graphite particles with polyvinylidene fluoride (PVDF) as binder. Intercalation of Li into graphite occurs in stages and produces anisotropic strains. As batteries have a fixed size and shape these strains are converted into mechanical stresses. Conventionally staging phenomena has been observed with X-ray diffraction and collaborated electrochemically with the potential. Work herein shows that staging is also clearly observed in stress. The Li staging potentials as measured by differential chronopotentiometry and stress are nearly identical. Relative peak heights of Li staging, as measured by these two techniques, are similar during reduction, but differ during oxidation due to non-linear stress relaxation phenomena. This stress relaxation appears to be due to homogenization of Li within graphite particles rather than viscous flow of the binder. The first Li reduction wave occurs simultaneously with formation of a passivating layer known as the solid electrolyte interphase (SEI). Preliminary experiments have shown the stress of SEI formation to be tensile (~+1.5 MPa).
ContributorsMickelson, Lawrence (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Buttry, Daniel (Committee member) / Venables, John (Committee member) / Arizona State University (Publisher)
Created2011
Description
Low temperature fuel cells are very attractive energy conversion technology for automotive applications due to their qualities of being clean, quiet, efficient and good peak power densities. However, due to high cost and limited durability and reliability, commercialization of this technology has not been possible as yet. The high fuel cell cost is mostly due to the expensive noble catalyst Pt. Alkaline fuel cell (AFC) systems, have potential to make use of non-noble catalysts and thus, provides with a solution of overall lower cost. Therefore, this issue has been addressed in this thesis work. Hydrogen-oxygen fuel cells using an alkaline anion exchange membrane were prepared and evaluated. Various non-platinum catalyst materials were investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201) and compared with commercial noble metal catalysts. Co and Fe phthalocyanine catalyst materials were synthesized using multi-walled carbon nanotubes (MWCNTs) as support materials. X-ray photoelectron spectroscopic study was conducted in order to examine the surface composition. The electroreduction of oxygen has been investigated on Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT and commercial Pt/C catalysts. The oxygen reduction reaction kinetics on these catalyst materials were evaluated using rotating disk electrodes in 0.1 M KOH solution and the current density values were consistently higher for Co phthalocyanine based electrodes compared to Fe phthalocyanine. The fuel cell performance of the MEAs with Co and Fe phthalocyanines and Tanaka Kikinzoku Kogyo Pt/C cathode catalysts were 100, 60 and 120 mW cm-2 using H22 and O2 gases. This thesis also includes work on synthesizing nitrogen doped MWCNTs using post-doping and In-Situ methods. Post-doped N-MWNCTs were prepared through heat treatment with NH4OH as nitrogen source. Characterization was done through fuel cell testing, which gave peak power density ~40mW.cm-2. For In-Situ N-MWCT, pyridine was used as nitrogen source. The sample characterization was done using Raman spectroscopy and RBS, which showed the presence ~3 at.% of nitrogen on the carbon surface.
ContributorsShah, QuratulAin Jawed (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Tamizhmani, Govindasamy (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2012
Description
A specific species of the genus Geobacter exhibits useful electrical properties when processing a molecule often found in waste water. A team at ASU including Dr Cèsar Torres and Dr Sudeep Popat used that species to create a special type of solid oxide fuel cell we refer to as a microbial fuel cell. Identification of possible chemical processes and properties of the reactions used by the Geobacter are investigated indirectly by taking measurements using Electrochemical Impedance Spectroscopy of the electrode-electrolyte interface of the microbial fuel cell to obtain the value of the fuel cell's complex impedance at specific frequencies. Investigation of the multiple polarization processes which give rise to measured impedance values is difficult to do directly and so examination of the distribution function of relaxation times (DRT) is considered instead. The DRT is related to the measured complex impedance values using a general, non-physical equivalent circuit model. That model is originally given in terms of a Fredholm integral equation with a non-square integrable kernel which makes the inverse problem of determining the DRT given the impedance measurements an ill-posed problem. The original integral equation is rewritten in terms of new variables into an equation relating the complex impedance to the convolution of a function based upon the original integral kernel and a related but separate distribution function which we call the convolutional distribution function. This new convolutional equation is solved by reducing the convolution to a pointwise product using the Fourier transform and then solving the inverse problem by pointwise division and application of a filter function (equivalent to regularization). The inverse Fourier transform is then taken to get the convolutional distribution function. In the literature the convolutional distribution function is then examined and certain values of a specific, less general equivalent circuit model are calculated from which aspects of the original chemical processes are derived. We attempted to instead directly determine the original DRT from the calculated convolutional distribution function. This method proved to be practically less useful due to certain values determined at the time of experiment which meant the original DRT could only be recovered in a window which would not normally contain the desired information for the original DRT. This limits any attempt to extend the solution for the convolutional distribution function to the original DRT. Further research may determine a method for interpreting the convolutional distribution function without an equivalent circuit model as is done with the regularization method used to solve directly for the original DRT.
ContributorsBaker, Robert Simpson (Author) / Renaut, Rosemary (Thesis director) / Kostelich, Eric (Committee member) / School of Mathematical and Statistical Sciences (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
In this Honors thesis, direct flame solid oxide fuel cells (DFFC) were considered for their feasibility in providing a means of power generation for remote powering needs. Also considered for combined heat and fuel cell power cogeneration are thermoelectric cells (TEC). Among the major factors tested in this project for all cells were life time, thermal cycle/time based performance, and failure modes for cells. Two types of DFFC, anode and electrolyte supported, were used with two different fuel feed streams of propane/isobutene and ethanol. Several test configurations consisting of single cells, as well as stacked systems were tested to show how cell performed and degraded over time. All tests were run using a Biologic VMP3 potentiostat connected to a cell placed within the flame of a modified burner MSR® Wisperlite Universal stove. The maximum current and power output seen by any electrolyte supported DFFCs tested was 47.7 mA/cm2 and 9.6 mW/cm2 respectively, while that generated by anode supported DFFCs was 53.7 mA/cm2 and 9.25 mW/cm2 respectively with both cells operating under propane/isobutene fuel feed streams. All TECs tested dramatically outperformed both constructions of DFFC with a maximum current and power output of 309 mA/cm2 and 80 mW/cm2 respectively. It was also found that electrolyte supported DFFCs appeared to be less susceptible to degradation of the cell microstructure over time but more prone to cracking, while anode supported DFFCs were dramatically less susceptible to cracking but exhibited substantial microstructure degradation and shorter usable lifecycles. TECs tested were found to only be susceptible to overheating, and thus were suggested for use with electrolyte supported DFFCs in remote powering applications.
ContributorsTropsa, Sean Michael (Author) / Torres, Cesar (Thesis director) / Popat, Sudeep (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
Description
Microbial fuel cells (MFCs) facilitate the conversion of organic matter to electrical current to make the total energy in black water treatment neutral or positive and produce hydrogen peroxide to assist the reuse of gray water. This research focuses on wastewater treatment at the U.S. military forward operating bases (FOBs). FOBs experience significant challenges with their wastewater treatment due to their isolation and dangers in transporting waste water and fresh water to and from the bases. Even though it is theoretically favorable to produce power in a MFC while treating black water, producing H2O2 is more useful and practical because it is a powerful cleaning agent that can reduce odor, disinfect, and aid in the treatment of gray water. Various acid forms of buffers were tested in the anode and cathode chamber to determine if the pH would lower in the cathode chamber while maintaining H2O2 efficiency, as well as to determine ion diffusion from the anode to the cathode via the membrane. For the catholyte experiments, phosphate and bicarbonate were tested as buffers while sodium chloride was the control. These experiments determined that the two buffers did not lower the pH. It was seen that the phosphate buffer reduced the H2O2 efficiency significantly while still staying at a high pH, while the bicarbonate buffer had the same efficiency as the NaCl control. For the anolyte experiments, it was shown that there was no diffusion of the buffers or MFC media across the membrane that would cause a decrease in the H2O2 production efficiency.
ContributorsThompson, Julia (Author) / Torres, Cesar (Thesis director) / Popat, Sudeep (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Hydrogen fuel cells have been previously investigated as a viable replacement to traditional gas turbine auxiliary power unit onboard fixed wing commercial jets. However, so far no study has attempted to extend their applicability to rotary wing aircrafts. To aid in the advancement of such innovative technologies, a holistic technical approach is required to ensure risk reduction and cost effectiveness throughout the product lifecycle. This paper will evaluate the feasibility of replacing a gas turbine auxiliary power unit on a helicopter with a direct hydrogen, air breathing, proton exchange membrane fuel cell, all while emphasizing a system engineering approach that utilize a specialized set of tools and artifacts.
ContributorsNesheiwat, Rod (Author) / Kannan, Arunachala M (Thesis advisor) / Nam, Changho (Committee member) / Mayyas, Abdel Ra'Ouf (Committee member) / Arizona State University (Publisher)
Created2016