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Novel anhydrous superprotonic ionic liquids and membranes for application in mid-temperature fuel cells

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…

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

Practicality of the Convolutional Solution Method of the Polarization Estimation Inverse Problem for Solid Oxide Fuel Cells

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…

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

Direct Flame Solid Oxide Fuel Cells for Use in Remote Powering Applications

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…

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

Characterizing Buffers to Maximize Peroxide Production in the Cathode Chamber of Microbial Fuel Cells

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).…

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

A new class of solid state, single-ion conductors (H+ and Li+): silicon-based plastic crystals

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…

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

Fuel Cell Integrated Gas Turbine Hybrid System Under Various Conditions

Description

A novel concept for integration of flame-assisted fuel cells (FFC) with a gas turbine is analyzed in this paper. Six different fuels (CH4, C3H8, JP-4, JP-5, JP-10(L), and H2) are investigated for the analytical model of the FFC integrated gas turbine hybrid system. As equivalence ratio increases, the efficiency of…

A novel concept for integration of flame-assisted fuel cells (FFC) with a gas turbine is analyzed in this paper. Six different fuels (CH4, C3H8, JP-4, JP-5, JP-10(L), and H2) are investigated for the analytical model of the FFC integrated gas turbine hybrid system. As equivalence ratio increases, the efficiency of the hybrid system increases initially then decreases because the decreasing flow rate of air begins to outweigh the increasing hydrogen concentration. This occurs at an equivalence ratio of 2 for CH4. The thermodynamic cycle is analyzed using a temperature entropy diagram and a pressure volume diagram. These thermodynamic diagrams show as equivalence ratio increases, the power generated by the turbine in the hybrid setup decreases. Thermodynamic analysis was performed to verify that energy is conserved and the total chemical energy going into the system was equal to the heat rejected by the system plus the power generated by the system. Of the six fuels, the hybrid system performs best with H2 as the fuel. The electrical efficiency with H2 is predicted to be 27%, CH4 is 24%, C3H8 is 22%, JP-4 is 21%, JP-5 is 20%, and JP-10(L) is 20%. When H2 fuel is used, the overall integrated system is predicted to be 24.5% more efficient than the standard gas turbine system. The integrated system is predicted to be 23.0% more efficient with CH4, 21.9% more efficient with C3H8, 22.7% more efficient with JP-4, 21.3% more efficient with JP-5, and 20.8% more efficient with JP-10(L). The sensitivity of the model is investigated using various fuel utilizations. When CH4 fuel is used, the integrated system is predicted to be 22.7% more efficient with a fuel utilization efficiency of 90% compared to that of 30%.

ContributorsRupiper, Lauren Nicole (Author) / Milcarek, Ryan (Thesis director) / Wang, Liping (Committee member) / Mechanical and Aerospace Engineering Program (Contributor) / School for Engineering of Matter,Transport & Enrgy (Contributor) / Barrett, The Honors College (Contributor)

Created2021-05

Analysis of Various Renewable Energy Systems as a Potential Replacement to Industrial Diesel Engine Systems [CLOSED DEFENSE]

Description

This thesis explores the investigation of the project “Designing for a Post-Diesel Engine World”, a collaborative experiment between organizations within Arizona State University and an undisclosed company. This investigation includes the analysis of various renewable energy technologies and their potential to replace industrial diesel engines as used in the company’s…

This thesis explores the investigation of the project “Designing for a Post-Diesel Engine World”, a collaborative experiment between organizations within Arizona State University and an undisclosed company. This investigation includes the analysis of various renewable energy technologies and their potential to replace industrial diesel engines as used in the company’s business. In order to be competitive with diesel engines, the technology should match or exceed diesel in power output, have reduced environmental impact, and meet other criteria standards as determined by the company. The team defined the final selection criteria as: low environmental impact, high efficiency, high power, and high technology readiness level. I served as the lead Hydrogen Fuel Cell Researcher and originally hypothesized that PEM fuel cells would be the most viable solution. Results of the analysis led to PEM fuel cells and Li-ion batteries being top contenders, and the team developed a hybrid solution incorporating both of these technologies in a technical and strategic solution. The resulting solution design from this project has the potential to be modified and implemented in various industries and reduce overall anthropogenic emissions from industrial processes.

ContributorsFernandez, Alexandra Marie (Author) / Heller, Cheryl (Thesis director) / Smith, Tyler (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)

Created2021-05

Fabricating Micro-Tubular Solid Oxide Fuel Cells and Studying the Kinetics of CO and H2 as Fuels

Description

One of the most promising technologies for creating power without emissions is Solid Oxide Fuel Cells (SOFC) because it uses oxygen and hydrogen to create electricity with the only byproduct being water. To figure out the optimal design of the fuel cell, a literature review was conducted to determine the…

One of the most promising technologies for creating power without emissions is Solid Oxide Fuel Cells (SOFC) because it uses oxygen and hydrogen to create electricity with the only byproduct being water. To figure out the optimal design of the fuel cell, a literature review was conducted to determine the effects of adding both internal and external current collectors as well as the difference length has on the performance. To learn more about the kinetics of the reaction, hydrogen and carbon monoxide disappearance rates were measured to compare the rate at which each species disappears.

ContributorsPhillips, Kristina (Author) / Milcarek, Ryan (Thesis director) / Wang, Robert (Committee member) / Barrett, The Honors College (Contributor) / Mechanical and Aerospace Engineering Program (Contributor)

Created2022-05

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