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- All Subjects: Fuel Cells
- Creators: Nam, Changho
- Creators: Richert, Ranko
Description
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
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
Description
Plastic crystals as a class are of much interest in applications as solid state electrolytes for electrochemical energy conversion devices. A subclass exhibit very high protonic conductivity and its members have been investigated as possible fuel cell electrolytes, as first demonstrated by Haile’s group in 2001 with CsHSO4. To date these have been inorganic compounds with tetrahedral oxyanions carrying one or more protons, charge-balanced by large alkali cations. Above the rotator phase transition, the HXO4- anions re-orient at a rate dependent on temperature while the centers of mass remain ordered. The transition is accompanied by a conductivity "jump" (as much as four orders of magnitude, to ~ 10 mScm-1 in the now-classic case of CsHSO4) due to mobile protons. These superprotonic plastic crystals bring a “true solid state” alternative to polymer electrolytes, operating at mild temperatures (150-200ºC) without the requirement of humidification. This work describes a new class of solid acids based on silicon, which are of general interest. Its members have extraordinary conductivities, as high as 21.5 mS/cm at room temperature, orders of magnitude above any previous reported case. Three fuel cells are demonstrated, delivering current densities as high as 225 mA/cm2 at short-circuit at 130ºC in one example and 640 mA/cm2 at 87ºC in another. The new compounds are insoluble in water, and their remarkably high conductivities over a wide temperature range allow for lower temperature operations, thus reducing the risk of hydrogen sulfide formation and dehydration reactions. Additionally, plastic crystals have highly advantageous properties that permit their application as solid state electrolytes in lithium batteries. So far only doped materials have been presented. This work presents for the first time non-doped plastic crystals in which the lithium ions are integral part of the structure, as a solid state electrolyte. The new electrolytes have conductivities of 3 to 10 mS/cm at room temperature, and in one example maintain a highly conductive state at temperatures as low as -30oC. The malleability of the materials and single ion conducting properties make these materials highly interesting candidates as a novel class of solid state lithium conductors.
ContributorsKlein, Iolanda Santana (Author) / Angell, Charles A (Thesis advisor) / Buttry, Daniel A (Committee member) / Richert, Ranko (Committee member) / Arizona State University (Publisher)
Created2016
Description
As electric powered unmanned aerial vehicles enter a new age of commercial viability, market opportunities in the small UAV sector are expanding. Extending UAV flight time through a combination of fuel cell and battery technologies enhance the scope of potential applications. A brief survey of UAV history provides context and examples of modern day UAVs powered by fuel cells are given. Conventional hybrid power system management employs DC-to-DC converters to control the power split between battery and fuel cell. In this study, a transistor replaces the DC-to-DC converter which lowers weight and cost. Simulation models of a lithium ion battery and a proton exchange membrane fuel cell are developed and integrated into a UAV power system model. Flight simulations demonstrate the operation of the transistor-based power management scheme and quantify the amount of hydrogen consumed by a 5.5 kg fixed wing UAV during a six hour flight. Battery power assists the fuel cell during high throttle periods but may also augment fuel cell power during cruise flight. Simulations demonstrate a 60 liter reduction in hydrogen consumption when battery power assists the fuel cell during cruise flight. Over the full duration of the flight, averaged efficiency of the power system exceeds 98%. For scenarios where inflight battery recharge is desirable, a constant current battery charger is integrated into the UAV power system. Simulation of inflight battery recharge is performed. Design of UAV hybrid power systems must consider power system weight against potential flight time. Data from the flight simulations are used to identify a simple formula that predicts flight time as a function of energy stored onboard the modeled UAV. A small selection of commercially available batteries, fuel cells, and compressed air storage tanks are listed to characterize the weight of possible systems. The formula is then used in conjunction with the weight data to generate a graph of power system weight versus potential flight times. Combinations of the listed batteries, fuel cells, and storage tanks are plotted on the graph to evaluate various hybrid power system configurations.
ContributorsStrele, Thomas (Author) / Nam, Changho (Thesis advisor) / Kannan, Arunachalanadar M (Committee member) / Pollat, Scott L (Committee member) / Arizona State University (Publisher)
Created2016
Temperature and polarizability effects on electron transfer in biology and artificial photosynthesis
Description
This study aims to address the deficiencies of the Marcus model of electron transfer
(ET) and then provide modifications to the model. A confirmation of the inverted energy
gap law, which is the cleanest verification so far, is presented for donor-acceptor complexes.
In addition to the macroscopic properties of the solvent, the physical properties of the solvent
are incorporated in the model via the microscopic solvation model. For the molecules
studied in this dissertation, the rate constant first increases with cooling, in contrast to the
prediction of the Arrhenius law, and then decreases at lower temperatures. Additionally,
the polarizability of solute, which was not considered in the original Marcus theory, is included
by the Q-model of ET. Through accounting for the polarizability of the reactants, the
Q-model offers an important design principle for achieving high performance solar energy
conversion materials. By means of the analytical Q-model of ET, it is shown that including
molecular polarizability of C60 affects the reorganization energy and the activation barrier
of ET reaction.
The theory and Electrochemistry of Ferredoxin and Cytochrome c are also investigated.
By providing a new formulation for reaction reorganization energy, a long-standing disconnect
between the results of atomistic simulations and cyclic voltametery experiments is
resolved. The significant role of polarizability of enzymes in reducing the activation energy
of ET is discussed. The binding/unbinding of waters to the active site of Ferredoxin leads
to non-Gaussian statistics of energy gap and result in a smaller activation energy of ET.
Furthermore, the dielectric constant of water at the interface of neutral and charged
C60 is studied. The dielectric constant is found to be in the range of 10 to 22 which is
remarkably smaller compared to bulk water( 80). Moreover, the interfacial structural
crossover and hydration thermodynamic of charged C60 in water is studied. Increasing the
charge of the C60 molecule result in a dramatic structural transition in the hydration shell,
which lead to increase in the population of dangling O-H bonds at the interface.
(ET) and then provide modifications to the model. A confirmation of the inverted energy
gap law, which is the cleanest verification so far, is presented for donor-acceptor complexes.
In addition to the macroscopic properties of the solvent, the physical properties of the solvent
are incorporated in the model via the microscopic solvation model. For the molecules
studied in this dissertation, the rate constant first increases with cooling, in contrast to the
prediction of the Arrhenius law, and then decreases at lower temperatures. Additionally,
the polarizability of solute, which was not considered in the original Marcus theory, is included
by the Q-model of ET. Through accounting for the polarizability of the reactants, the
Q-model offers an important design principle for achieving high performance solar energy
conversion materials. By means of the analytical Q-model of ET, it is shown that including
molecular polarizability of C60 affects the reorganization energy and the activation barrier
of ET reaction.
The theory and Electrochemistry of Ferredoxin and Cytochrome c are also investigated.
By providing a new formulation for reaction reorganization energy, a long-standing disconnect
between the results of atomistic simulations and cyclic voltametery experiments is
resolved. The significant role of polarizability of enzymes in reducing the activation energy
of ET is discussed. The binding/unbinding of waters to the active site of Ferredoxin leads
to non-Gaussian statistics of energy gap and result in a smaller activation energy of ET.
Furthermore, the dielectric constant of water at the interface of neutral and charged
C60 is studied. The dielectric constant is found to be in the range of 10 to 22 which is
remarkably smaller compared to bulk water( 80). Moreover, the interfacial structural
crossover and hydration thermodynamic of charged C60 in water is studied. Increasing the
charge of the C60 molecule result in a dramatic structural transition in the hydration shell,
which lead to increase in the population of dangling O-H bonds at the interface.
ContributorsWaskasi, Morteza M (Author) / Matyushov, Dmitry (Thesis advisor) / Richert, Ranko (Committee member) / Heyden, Matthias (Committee member) / Beckstein, Oliver (Committee member) / Arizona State University (Publisher)
Created2019