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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

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.
ContributorsKolli, Sri Harsha (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Nam, Changho (Committee member) / Peng, Xihong (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Gas diffusion layers (GDLs) are a critical and essential part of proton exchange membrane fuel cells (PEMFCs). They carry out various important functions such as transportation of reactants to and from the reaction sites. The material properties and structural characteristics of the substrate and the microporous layer strongly influence fuel

Gas diffusion layers (GDLs) are a critical and essential part of proton exchange membrane fuel cells (PEMFCs). They carry out various important functions such as transportation of reactants to and from the reaction sites. The material properties and structural characteristics of the substrate and the microporous layer strongly influence fuel cell performance. The microporous layer of the GDLs was fabricated with the carbon slurry dispersed in water containing ammonium lauryl sulfate (ALS) using the wire rod coating method. GDLs were fabricated with different materials to compose the microporous layer and evaluated the effects on PEMFC power output performance. The consistency of the carbon slurry was achieved by adding 25 wt. % of PTFE, a binding agent with a 75:25 ratio of carbon (Pureblack and vapor grown carbon fiber). The GDLs were investigated in PEMFC under various relative humidity (RH) conditions using H2/O2 and H2/Air. GDLs were also fabricated with the carbon slurry dispersed in water containing sodium dodecyl sulfate (SDS) and multiwalled carbon nanotubes (MWCNTs) with isopropyl alcohol (IPA) based for fuel cell performance comparison. MWCNTs and SDS exhibits the highest performance at 60% and 70% RH with a peak power density of 1100 mW.cm-2 and 850 mW.cm-2 using air and oxygen as an oxidant. This means that the gas diffusion characteristics of these two samples were optimum at 60 and 70 % RH with high limiting current density range. It was also found that the composition of the carbon slurry, specifically ALS concentration has the highest peak power density of 1300 and 500mW.cm-2 for both H2/O2 and H2/Air at 100% RH. However, SDS and MWCNTs demonstrates the lowest power density using air and oxygen as an oxidants at 100% RH.
ContributorsVillacorta, Rashida (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Peng, Xihong (Committee member) / Tamizhmani, Govindasamy (Committee member) / Arizona State University (Publisher)
Created2012
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Description
With a recent shift to a more environmentally conscious society, low-carbon and non-carbon producing energy production methods are being investigated and applied all over the world. Of these methods, fuel cells show great potential for clean energy production. A fuel cell is an electrochemical energy conversion device which directly converts

With a recent shift to a more environmentally conscious society, low-carbon and non-carbon producing energy production methods are being investigated and applied all over the world. Of these methods, fuel cells show great potential for clean energy production. A fuel cell is an electrochemical energy conversion device which directly converts chemical energy into electrical energy. Proton exchange membrane fuel cells (PEMFCs) are a highly researched energy source for automotive and stationary power applications. In order to produce the power required to meet Department of Energy requirements, platinum (Pt) must be used as a catalyst material in PEMFCs. Platinum, however, is very expensive and extensive research is being conducted to develop ways to reduce the amount of platinum used in PEMFCs. In the current study, three catalyst synthesis techniques were investigated and evaluated on their effectiveness to produce platinum-on copper (Pt@Cu) core-shell nanocatalyst on multi-walled carbon nanotube (MWCNT) support material. These three methods were direct deposition method, two-phase surfactant method, and single-phase surfactant method, in which direct deposition did not use a surfactant for particle size control and the surfactant methods did. The catalyst materials synthesized were evaluated by visual inspection and fuel cell performance. Samples which produced high fuel cell power output were evaluated using transmission electron microscopy (TEM) imaging. After evaluation, it was concluded that the direct deposition technique was effective in synthesizing Pt@Cu core-shell nanocatalyst on MWCNTs support when a rinsing process was used before adding platinum. The peak power density achieved by the rinsed core-shell catalyst was 618 mW.cm-2 , 13 percent greater than that of commercial platinum-carbon (Pt/C) catalyst. Transmission electron microscopy imaging revealed the core-shell catalyst contained Pt shells and platinum-copper alloy cores. Rinsing with deionized (DI) water was shown to be a crucial step in core-shell catalyst deposition as it reduced the number of platinum colloids on the carbon nanotube surface. After evaluation, it was concluded that the two-phase surfactant and single-phase surfactant synthesis methods were not effective at producing core-shell nanocatalyst with the parameters investigated.
ContributorsAdame, Anthony (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Peng, Xihong (Committee member) / Tamizhmani, Govindasamy (Committee member) / Arizona State University (Publisher)
Created2012
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Description

Lithium ion batteries are quintessential components of modern life. They are used to power smart devices — phones, tablets, laptops, and are rapidly becoming major elements in the automotive industry. Demand projections for lithium are skyrocketing with production struggling to keep up pace. This drive is due mostly to the

Lithium ion batteries are quintessential components of modern life. They are used to power smart devices — phones, tablets, laptops, and are rapidly becoming major elements in the automotive industry. Demand projections for lithium are skyrocketing with production struggling to keep up pace. This drive is due mostly to the rapid adoption of electric vehicles; sales of electric vehicles in 2020 are more than double what they were only a year prior. With such staggering growth it is important to understand how lithium is sourced and what that means for the environment. Will production even be capable of meeting the demand as more industries make use of this valuable element? How will the environmental impact of lithium affect growth? This thesis attempts to answer these questions as the world looks to a decade of rapid growth for lithium ion batteries.

ContributorsMelton, John (Author) / Brian, Jennifer (Thesis director) / Karwat, Darshawn (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
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Description
The fuel cell is a promising device that converts the chemical energy directly into the electrical energy without combustion process. However, the slow reaction rate of the oxygen reduction reaction (ORR) necessitates the development of cathode catalysts for low-temperature fuel cells. After a thorough literature review in Chapter 1, the

The fuel cell is a promising device that converts the chemical energy directly into the electrical energy without combustion process. However, the slow reaction rate of the oxygen reduction reaction (ORR) necessitates the development of cathode catalysts for low-temperature fuel cells. After a thorough literature review in Chapter 1, the thesis is divided into three parts as given below in Chapters 2-4.

Chapter 2 describes the study on the Pt and Pt-Me (Me: Co, Ni) alloy nanoparticles supported on the pyrolyzed zeolitic imidazolate framework (ZIF) towards ORR. The Co-ZIF and NiCo-ZIF were synthesized by the solvothermal method and then mixed with Pt precursor. After pyrolysis and acid leaching, the PtCo/NC and PtNiCo/NC were evaluated in proton exchange membrane fuel cells (PEMFC). The peak power density exhibited > 10% and 15% for PtCo/NC and PtNiCo/NC, respectively, compared to that with commercial Pt/C catalyst under identical test conditions.

Chapter 3 is the investigation of the oxygen vacancy (OV) effect in a-MnO2 as a cathode catalyst for alkaline membrane fuel cells (AMFC). The a-MnO2 nanorods were synthesized by hydrothermal method and heated at 300, 400 and 500 ℃ in the air to introduce the OV. The 400 ℃ treated material showed the best ORR performance among all other samples due to more OV in pure a-MnO2 phase. The optimized AMFC electrode showed ~ 45 mW.cm-2, which was slightly lower than that with commercial Pt/C (~60 mW.cm-2).

Chapter 4 is the density functional theory (DFT) study of the protonation effect and active sites towards ORR on a-MnO2 (211) plane. The theoretically optimized oxygen adsorption and hydroxyl ion desorption energies were ~ 1.55-1.95 eV and ~ 0.98-1.45 eV, respectively, by Nørskov et al.’s calculations. All the configurations showed oxygen adsorption and hydroxyl ion desorption energies were ranging from 0.27 to 1.76 eV and 1.59 to 15.0 eV, respectively. The site which was close to two Mn ions showed the best oxygen adsorption and hydroxyl ion desorption energies improvement with the surface protonation.

Based on the results given in Chapters 1-4, the major findings are summarized in Chapter 5.
ContributorsShi, Xuan, Ph.D (Author) / Kannan, Arunachalanadar Mada (Thesis advisor) / Liu, Jingyue (Committee member) / Nam, Changho (Committee member) / Peng, Xihong (Committee member) / Arizona State University (Publisher)
Created2019
Description
Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for future energy storage devices. Electrode materials that alloy with Li, such as Si, are one of the most promising alternatives for Li-ion battery anodes due to their high capacities. Tetrel (Si,

Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for future energy storage devices. Electrode materials that alloy with Li, such as Si, are one of the most promising alternatives for Li-ion battery anodes due to their high capacities. Tetrel (Si, Ge, Sn) clathrates are a class of host-guest crystalline structures in which Tetrel elements form a cage framework and encapsulate metal guest atoms. These structures can form with defects such as framework/guest atom substitutions and vacancies which result in a wide design space for tuning materials properties. The goal of this work is to establish structure property relationships within the context of Li-ion battery anode applications. The type I Ba 8 Al y Ge 46-y clathrates are investigated for their electrochemical reactions with Li and show high capacities indicative of alloying reactions. DFT calculations show that Li insertion into the framework vacancies is favorable, but the migration barriers are too high for room temperature diffusion. Then, guest free type I clathrates are investigated for their Li and Na migration barriers. The results show that Li migration in the clathrate frameworks have low energy barriers (0.1- 0.4 eV) which suggest the possibility for room temperature diffusion. Then, the guest free, type II Si clathrate (Na 1 Si 136 ) is synthesized and reversible Li insertion into the type II Si clathrate structure is demonstrated. Based on the reasonable capacity (230 mAh/g), low reaction voltage (0.30 V) and low volume expansion (0.21 %), the Si clathrate could be a promising insertion anode for Li-ion batteries. Next, synchrotron X-ray measurements and pair distribution function (PDF) analysis are used to investigate the lithiation pathways of Ba 8 Ge 43 , Ba 8 Al 16 Ge 30 , Ba 8 Ga 15 Sn 31 and Na 0.3 Si 136 . The results show that the Ba-clathrates undergo amorphous phase transformations which is distinct from their elemental analogues (Ge, Sn) which feature crystalline lithiation pathways. Based on the high capacities and solid-solution reaction mechanism, guest-filled clathrates could be promising precursors to form alloying anodes with novel electrochemical properties. Finally, several high temperature (300-550 °C) electrochemical synthesis methods for Na-Si and Na-Ge clathrates are demonstrated in a cell using a Na β’’-alumina solid electrolyte.
ContributorsDopilka, Andrew (Author) / Chan, Candace K (Thesis advisor) / Zhuang, Houlong (Committee member) / Peng, Xihong (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2021
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Description
In the present study, primarily, gas diffusion layer samples containing microporous layers (MPLs), are fabricated using carbon paper substrate, PUREBLACK® carbon powder and polyethylene glycol (PEG) as pore forming agent. The GDLs are studied in single cell fuel cell, to evaluate the effect of porosity of the micro-porous layer on

In the present study, primarily, gas diffusion layer samples containing microporous layers (MPLs), are fabricated using carbon paper substrate, PUREBLACK® carbon powder and polyethylene glycol (PEG) as pore forming agent. The GDLs are studied in single cell fuel cell, to evaluate the effect of porosity of the micro-porous layer on the performance at different operating relative humidity conditions and compared with commercial GDLs. Scanning electron microscopy (SEM) and contact angle measurements indicate crack-free surface morphology and hydrophobic characteristics of the PUREBLACK® based GDLs, respectively. By varying the wt. % of PEG, fuel cell performance is evaluated under relative humidity conditions of 60 and 100 % using H2/O2 and H2/Air at 70 oC and the durability is also evaluated for the samples without, with 30% PEG and commercial. The fuel cell performance of the GDL with 30 % PEG (with pore volume 1.72 cc.g-1) exhibited higher performance (444 and 432 mW.cm-2 at 60 and 100 % RH conditions, respectively using H2 and air) compared to that without pore forming agent (436 and 397 mW.cm-2).Subsequently, the best performing configuration underwent two different ex-situ methods of accelerated stress testing (AST), in water and hydrogen peroxide (30%), for 1000 and 24 h, respectively. The samples were evaluated via contact angle, SEM, and fuel cell performance, before and after the ASTs, and compared to similar configuration, using carbon powder VULCAN® (XC-72R), and aged in the exact same conditions. Contact angle and SEM demonstrated greater degradation of VULCAN® carbon, especially in hydrogen peroxide, where carbon corrosion caused surface cracks and change in hydrophobicity. The fuel cell performance and durability, evaluated at 60 and 100% RH at 70 oC, using O2 and air as oxidants, confirmed that VULCAN® carbon is more prone to carbon corrosion, with significant performance loss (12-19%) in contrast to PUREBLACK® that demonstrated higher carbon corrosion resistance due to its graphitized surface.
ContributorsAthanasaki, Grigoria (Author) / Kannan, Arunachala Mada A. M. (Thesis advisor) / Nam, Changho (Committee member) / Peng, Xihong (Committee member) / Arizona State University (Publisher)
Created2021