Fuel cells, hydrogen, polymer electrolyte membrane, pem, proton exchange membrane, nafion, perfluorosulfonic acid, degradation, degradation mechanisms, accelerated durability, fenton test, ocv hold, fluoride emission, platinum band, degradation mitigation, radical scavengers, cerium oxide, ceria, nanoparticles


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.


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Graduation Date





Hampton, Michael


Doctor of Philosophy (Ph.D.)


College of Sciences



Degree Program









Release Date

June 2014

Length of Campus-only Access

1 year

Access Status

Doctoral Dissertation (Open Access)


Dissertations, Academic -- Sciences, Sciences -- Dissertations, Academic

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Chemistry Commons