Per-Fluoro-Sulphonic-Acid (PFSA) ionomers have been singled out as the preferable ionomers for making the Polymer Electrolyte Membrane Fuel Cells (PEMFC) membranes owing to their extensive intrinsic chemical stability and super sulfonic acid strength which is core to the PEMFC proton conductivity. This thesis presents a deeper analysis into these PFSA ionomer membrane electrode assemblies (MEA), presenting an electrochemical-analytical comparative analysis of the two basic types, which are the Long-Side-Chain (LSC) Nafion® and the ShortSide-Chain (SSC) Aquivion® ionomer MEA with emphasis on performance and durability which are currently not well understood. In particular, electrochemical circuit models and semiempirical models were employed to enable distinguishable comparative analysis. Also, in this thesis, we present a further probe into the effect of ionomer ink making processes, critically investigating the effect of the High Share Dispersion (HSD) process on both the Nafion® and Aquivion® ionomer membrane electrode assembly (MEA). The findings in this research provides a valuable insight into the performance and durability of PFSA ionomer membrane under various application criteria. The effect of operating parameters and accelerated stress testing (AST) on the PFSA ionomers was determined using electrochemical impedance spectroscopy (EIS) and electronic circuit model (ECM) analysis. The result of this study, shows that the ionomer ink making process for Nafion® and Aquivion® MEAs are not transferrable. Analysis of the PEMFC performance upon application of the high shear dispersion (HSD) process showed that Nafion® MEA had a 10.47% increase in voltage while the Aquivion® MEA had a 2.53% decrease in voltage at current density of 1.14A/cm2 . Also, upon accelerated stress testing, the Nafion® showed a 10.49% increase in its voltage while the Aquivion® on the other hand had a 7.16% decrease in voltage at 0.66A/cm2 . Thus indicating the HSD process enhances the performance of the Nafion® MEA and inhibits the performance of the Aquivion® MEA.

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A novel free radical-based substitution reaction was developed for grafting aromatic/heteroaromatic compounds to perfluorosulfonic acid polymers (PFSAs). Two proton-exchange membranes perfluorobenzoic acid (PFBA) and perfluorobenzenesulfonic acid (PFBSA)—were synthesized for proton-exchange membrane fuel cells via the free radical-based reaction. The physical properties, in-plane ionic conductivities and fuel cell performance of two membranes were investigated. They exhibited different electrochemical and physical properties, possibly due to the formation of unique dimerized/trimerized structure of –CO2H groups in the PFBA membrane. A free radical-based thermolytic reaction under a high temperature (180 oC)/pressure (1000 psi) condition in the presence of TFA and hydrogen peroxide is first demonstrated. A novel perfluorotetrafluoroaniline (PFTFAn) polymer was synthesized from PFSA and 2,3,5,6-tetrafluoroaniline in one step via the thermolytic reaction. After doping H2SO4 in the PFTFAn polymer, a new conjugated acid membrane (H2SO4-doped PFTFAn) was obtained. The H2SO4-doped PFTFAn membrane displayed better chemical stability and mechanical properties than NafionTM due to the removal of –SO3H groups. The second part of this thesis deals with fluoropolymer-based anion-exchange membranes. A new class of coordinated metal/perfluoropolymer type composite membranes were synthesized and characterized for anion-exchange membrane fuel cells (AEMFCs). A membrane comprised of perfluoro(phenyl-2,2’:6’,2”-terpyridine) polymer, ZrO(ClO4)2 nanoclusters, and 2,2’:6’,2”-terpyridine displayed the highest conductivity of 23.1 mS/cm at 60 oC. The chemical stability test of composite membrane showed no conductivity loss after refluxing in 7 M KOH solution at 120 oC for 2,200 h. A H+ coordinated cage-shape molecule with a benzyl group (Bn-proton cage) was designed and synthesized as a base-stable anion-exchange group. By employing the free radical-based reaction, Bn-proton cage was grafted to a fluoropolymer to yield a stable anion-conductive membrane under alkaline conditions. The third part of this thesis is our design, synthesis and test of ionic liquids for reversible SO2 absorption. Novel di-cationic ionic liquids (DILs) were designed and synthesized for SO2 absorption. DILs were found to have better SO2 absorption capabilities than mono-cationic ionic liquids (MILs). A chloride-based DIL comprised of two N-methylimidazolium cations and a PEG9 (HO-(CH2CH2O)9-H) chain could reversibly uptake 3.710 mole SO2 per mole DIL under ambient conditions. The anion, temperature and water impact on SO2 absorption in DILs was investigated. Although replacing chloride with triflate or tosylate groups led to a reduced SO2 absorption for the DILs, a high selectivity against CO2 was observed in CO2 absorption test.

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Climate change has propelled the development of alternative power sources that minimize the emission of greenhouse effect gases. Widespread commercialization of polymer electrolyte membrane fuel cell (PEM-FC) technology for transportation and stationary applications requires cost-competitiveness with improved durability and performance. Advantages compared to battery electric vehicles include fast refueling and long distance range. One way to improve performance and minimize costs of PEM-FC involves the optimization of the nanostructure of the catalyst layer. The rate limiting oxygen reduction reaction occurs at a triple-phase interface in the cathode catalyst layer (CL) between the proton conductor perfluorosulfonic acid, PFSA, the Pt catalyst particles decorating the electron conductor carbon support and gaseous O2 available through the porous framework of the carbon support. Visualization and quantitation of the distribution of components in the CL requires microscopy techniques. Electron and X-ray microscopy have been used to characterize the distribution of the PFSA relative to the carbon support and porosity in CLs. Understanding and limiting the analytical impact of radiation damage, which occurs due to the ionizing nature of electrons and X-rays, is needed to improve quantitation, particularly of PFSA. This thesis developed scanning transmission X-ray microscopy (STXM) methods for quantitation of damage due to electron and soft X-ray irradiation in PFSA materials. Chemical damage to PFSA when irradiated by photons and electrons is dominated by fluorine loss and CF2-CF2 amorphization. The quantitative results are used to set maximum dose limits to help optimize characterization and quantitation of PFSA in fuel cell cathode catalyst layers using: analytical electron microscopy, X-ray microscopy, spectromicroscopy, spectrotomography, spectroptychography and spectro-ptycho-tomography. / Thesis / Doctor of Philosophy (PhD) / Polymer electrolyte membrane fuel cells are an alternative, environmentally friendly power source for transportation and stationary applications. Major challenges for mass production include cost competitiveness, improved durability and performance. A key component to enhance the performance and lower costs involves understanding and improving the spatial distribution of the perfluorosulfonic acid (PFSA) polymer in the catalyst layer. The ionizing nature of electrons and X-rays used in microscopy characterization tools challenges PFSA characterization since this material is radiation sensitive. This thesis developed measurement protocols and methods for quantitative studies of radiation damage to PFSA and other polymers using scanning transmission X-ray microscopy. The chemical changes to PFSA films irradiated with photons, electrons and ultraviolet (UV) photons were studied. The quantitative results identify limits to analytical electron and soft X-ray microscopy characterization of PFSA. The results are used to optimize methods for soft X-ray microscopy characterization of PFSA in fuel cell applications.

Les ionomères aromatiques sont considérés comme une alternative prometteuse à Nafion pour les PEMFCs en raison de leur bonne stabilité à l'oxydation, d'excellentes propriétés thermomécaniques et de faibles coûts, etc. La plupart des ionomères aromatiques sulfonés rapportés au cours des dernières décennies présentent cependant des performances inférieures à celles de Nafion. Avec une capacité d'échange ionique (CEI) similaire, d'une part, les ionomères aromatiques sont beaucoup moins conducteurs que Nafion, notamment à faible humidité relative. Les ionomères aromatiques ayant une CEI suffisante pour donner une conductivité équivalente à celle de Nafion, d'autre part, présentent un comportement excessivement gonflant dans l'eau. Les inconvénients des ionomères aromatiques sulfonés proviennent de (i) la répartition aléatoire de groupes acides sur un squelette de polymère rigide conduisant à une séparation hydrophile-hydrophobe faible, (ii) la proximité de fractions conductrices de protons à la chaîne principale de polymère conduisant à une nanostructure basse de composés ioniques, et (iii) la faible acidité de l'acide arylsulfonique. Dans le but de surmonter ces inconvénients, mon travail de doctorat se concentre sur le développement de nouveaux ionomères aromatiques avec une morphologie et des propriétés améliorées grâce à la conception de l'architecture moléculaire, en combinaison avec une condition optimisée de traitement de la membrane. A base de cet objectif, deux séries d'ionomères aromatiques à base de copoly (arylène éther sulfone) partiellement fluoré portant des chaînes latérales pendantes d'acide perfluorosulfonique (séries InX/Y) ou perfluorosulfonimide (SiX/Y) ont été développées et caractérisées. De plus, les PEM basés sur le mélange Nafion/InX/Y ont également été ciblés. Une grande attention a été portée à l'optimisation de l'état de traitement des membranes et à l'élucidation de la relation structure-morphologie-propriété des matériaux. / Aromatic ionomers are considered as a promising alternative to Nafion for PEMFCs due to their good oxidative stability, excellent thermomechanical properties, and low cost, etc. Most sulfonated aromatic ionomers reported over the past decades, however, show lower performance than that of Nafion. With similar ion-exchange capacity (IEC), on one hand, aromatic ionomers are much less conductive than Nafion, notably at low relative humidity. Aromatic ionomers with sufficient IEC to give equivalent conduction to that of Nafion, on the other hand, exhibit excessively swelling behavior in water. The shortcomings of sulfonated aromatic ionomers derive from (i) the random distribution of acidic groups on rigid polymer backbone leading to poor hydrophilic-hydrophobic separation, (ii) the proximity of proton-conducting moieties to the polymer main chain resulting in low nanostructure of ionic clusters, and (iii) the low acidity of aryl sulfonic acid. With the aim of overcoming these drawbacks, my PhD work focuses on developing new aromatic ionomers with improved morphology and properties via molecular architecture design, in combination with optimized membrane processing condition. Based on this objective, two series of aromatic ionomers based on partially-fluorinated multi-block copoly(arylene ether sulfone)s bearing pendant perfluorosulfonic acid (InX/Y series) or perfluorosulfonimide (SiX/Y series) side chains have been developed and characterized. Moreover, PEMs based on Nafion/InX/Y blend have also been focused. Much attention has been paid to optimizing the membrane processing condition and elucidating the structure-morphology-property relation in these materials.

Over the past three decades, the steady decrease in fossil energy resources, combined with a sustained increase in the demand for clean energy, has led the scientific community to develop new ways to produce energy. As is well known, one of the main challenges to overcome with fossil fuel-based energy sources is the reduction or even elimination of pollutant gases in the atmosphere. Although some advances have helped to slow the emission of greenhouse gases into the atmosphere (e.g., electric cars and more fuel-efficient gas-burning automobiles), most experts agree that it is not enough. Proton Exchange Membrane (PEM) fuel cells have been widely recognized as a potentially viable alternative for portable and stationary power generation, as well as for transportation. However, the widespread commercialization Proton Exchange Membrane Fuel Cells (PEMFCs) involves a thorough understanding of complex scientific and technological issues. This study investigated the various structure-property relationships and materials durability parameters associated with PEMFC development. First, the correlation between perfluorinated ionomer membranes and processing/performance issues in fuel cell systems was investigated. As confirmed by small-angle X-ray scattering data, impedance analysis, and dynamic mechanical analysis, solution processing with mixed organic-inorganic counterions was found to be effective in producing highly arranged perfluorinated sulfonic acid ionomer (PFSI) membranes with more favorable organization of the ionic domain. Moreover, thermal annealing was shown to enhance the proton mobility, thereby facilitating reorganization of the polymer backbone and the hydrophilic region for improved crystallinity and proton transport properties. This research also confirmed an increase in water uptake in the solution-processed membranes under investigation, which correlated to an increase in proton conductivity. Thus, annealing and solution-processing techniques were shown to be viable ways for controlling morphology and modulating the properties/performance of PFSI membranes. Second, this study investigated the role of the morphology on water and proton transport in perfluorinated ionomers. When annealed at high temperatures, a significant decrease in water uptake and an increase in crystallinity were observed, both of which are detrimental to fuel cell performance. Additionally, controlling the drying process was found to be crucial for optimizing the properties and performance of these membranes, since drying at temperatures close or above the α-relaxation temperature causes a major reorganization within the ionic domains. Third, although many investigations have looked at key PEMFC components, (e.g., the membrane, the catalyst, and the bipolar plates), there have been few studies of more "minor" components—namely, the performance and durability of seals, sealants, and adhesives, which are also exposed to harsh environmental conditions. When seals degrade or fail, reactant gases leak or are mixed, it can degrade the membrane electrode assembly (MEA), leading to a performance decrease in fuel cell stack performance. This portion of the research used degradation studies of certain proprietary elastomeric materials used as seals to investigate their overall stability and performance in fuel cell environments with applied mechanical stresses. Additionally, characterization of the mechanical and viscoelastic properties of these materials was conducted in order to predict the durability based on accelerated aging simulations as well. Continuous stress relaxation (CSR) characterization was performed on molded seals over a wide range of aging conditions using a customized CSR fixture. The effects of temperature, stress, and environmental conditions are reported in terms of changes in momentary and stress relaxations, chain scission and secondary crosslink formation. Aging studies provided insights on how anti-degradants or additives affect the performance and properties of sealing materials, as well as how a variety of environmental considerations might be improved to extend the lifetime of these elastomers. / Ph. D.

Fuel cells are known for their high efficiency and have the potential to become a major technology for producing clean energy, especially when the fuel, e.g. hydrogen, is produced from renewable energy sources such as wind or solar. Currently, the two main obstacles to wide-spread commercialization are their high cost and the short operational lifetime of certain components. Polymer electrolyte membrane (PEM) fuel cells have been a focus of attention in recent years, due to their use of hydrogen as a fuel, their comparatively low operating temperature and flexibility for use in both stationary and portable (automotive) applications. Perfluorosulfonic acid membranes are the leading ionomers for use in PEM hydrogen fuel cells. They combine essential qualities, such as high mechanical and thermal stability, with high proton conductivity. However, they are expensive and currently show insufficient chemical stability towards radicals formed during fuel cell operation, resulting in degradation that leads to premature failure. The incorporation of durability improving additives into perfluorosulfonic acid membranes is discussed in this work. iv Cerium oxide (ceria) is a well-known radical scavenger that has been used in the biological and medical field. It is able to quench radicals by facilely switching between its Ce(III) and Ce(IV) oxidation states. In this work, cerium oxide nanoparticles were added to perfluorosulfonic acid membranes and subjected to ex-situ and in-situ accelerated durability tests. The two ceria formulations, an in-house synthesized and commercially available material, were found to consist of crystalline particles of 2 – 5 nm and 20 – 150 nm size, respectively, that did not change size or shape when incorporated into the membranes. At higher temperature and relative humidity in gas flowing conditions, ceria in membranes is found to be reduced to its ionic form by virtue of the acidic environment. In ex-situ Fenton testing, the inclusion of ceria into membranes reduced the emission of fluoride, a strong indicator of degradation, by an order of magnitude with both liquid and gaseous hydrogen peroxide. In open-circuit voltage (OCV) hold fuel cell testing, ceria improved durability, as measured by several parameters such as OCV decay rate, fluoride emission and cell performance, over several hundred hours and influenced the formation of the platinum band typically found after durability testing.