|Title||Self-Assembly and Transport Limitations in Confined Nafion Films|
|Publication Type||Journal Article|
|Year of Publication||2013|
|Authors||Modestino, Miguel A., Devproshad K. Paul, Shudipto Dishari, Stephanie A. Petrina, Frances I. Allen, Michael A. Hickner, Kunal Karan, Rachel Segalman, and Adam Z. Weber|
|Pagination||867 - 873|
Ion-conducting polymers are important materials for a variety of electrochemical applications. Perfluorinated ionomers, such as Nafion, are the benchmark materials for proton conduction and are widely used in fuel cells and other electrochemical devices including solar-fuel generators, chlor-alkali cells, and redox flow batteries. While the behavior of Nafion in bulk membranes (10 to 100s ?m thick) has been studied extensively, understanding its properties under thin-film confinement is limited. Elucidating the behavior of thin Nafion films is particularly important for the optimization of fuel-cell catalyst layers or vapor-operated solar-fuel generators, where a thin film of ionomer is responsible for the transport of ions to and from the active electrocatalytic centers. Using a combination of transport-property measurements and structural characterization, this work demonstrates that confinement of Nafion in thin films induced thickness-dependent proton conductivity and ionic-domain structure. Confining Nafion films to thicknesses below 50 nm on a silicon substrate results in a loss of microphase separation of the hydrophilic and hydrophobic domains, which drastically increases the material?s water uptake while in turn decreasing its ionic conductivity.