Using Neutron Reflectometry to Quantify the Carbon-Nafion Interface for Proton Exchange Membrane Fuel Cell Applications
Authors: Randall Corey R. , Dura Joseph , Zou Lianfeng , Chen-Glasser Melodie , DeCaluwe Steven C. 
Published: July 2022

Due to its chemical stability in acidic environments and high ionic conductivity, Nafion has proven to be an essential material in proton exchange membrane fuel cell (PEMFC) designs. Nafion functions as both a membrane – separating the two electrodes – and as a conductive binder in each catalyst layer (CL). Nano-thin films of Nafion ionomer allow protons to reach carbon-supported Pt catalysts. In addition to protons, oxygen and water also move through the nano-thin Nafion ionomer to and from reactive Pt sites. These physical transport processes directly impact PEMFC performance. Therefore, measuring and determining ways to improve upon each of these processes is critical in the development of high performance PEMFCs.

In regards to thick Nafion membranes, conductivity and diffusion measurements can be readily performed in most laboratories. Nano-thin Nafion films on the other hand prove more challenging to study due to experimental limitations. Nevertheless, neutron reflectometry (NR) has been reported in literature as a capable technique to provide simultaneous quantitative structural and composition profiles for thin-film Nafion [1-5]. Results for Nafion at native silicon oxide interfaces show complex multi-layered structures forming distinct water-rich and water-poor regions [1-3]. Despite these advancements in our understanding of thin-film Nafion, it is still unclear how these observed structures may impact PEMFC performance. This is because silicon does not interface with Nafion in PEMFC CLs. Instead, carbon and Pt are the primary and secondary materials that interface with the thin-film ionomer. In the latter case, thin-film Nafion at Pt interfaces has been briefly studied in literature and shows significantly less structure than Nafion at silicon oxide interfaces [4,5]. Beyond the limited number of studies for Pt-Nafion interfaces, carbon-Nafion interface studies are even more scarce in literature [5]. This is likely because carbon black (i.e. the electron conductor in PEMFC CLs) is too rough to be used with NR. Therefore, to confidently assume the structure of Nafion at carbon black interfaces, trends from NR work on other carbon-based samples need to be compiled and compared, while considering their bonding structures and surface chemistries.

In this work, we extend the understanding of thin-film Nafion at carbon interfaces by testing four different carbon-based substrates. Using thin-film Nafion (< 100 nm) deposited on each carbon sample, NR was performed in both dry and humidified environments. Fitting the data to these experiments, results suggest a variety of polymer structures at the carbon-Nafion interface. These include complex multi-layered structures, similar to those at silicon oxide interfaces, as well as simple homogenous films with little-to-no interfacial structure. During this presentation, the implications of these results on species transport in PEMFC CLs will be discussed. Additionally, PEMFC performance predictions that incorporate learnings from this study will be made using an extended model from our earlier work [6].

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[2] J.A. Dura, V.S. Murthi, M. Hartman, S.K. Satija, and C.F. Majkrzak, “Multilamellar Interface Structures in Nafion,” Macromolecules, vol. 42, no. 13, pp. 4769–4774, 2009.

[3] U.N. Shrivastava, H. Fritzsche, and K. Karan, “Interfacial and Bulk Water in Ultrathin Films of Nafion, 3M PFSA, and 3M PFIA Ionomers on a Polycrystalline Platinum Surface,” Macromolecules, vol. 51, no. 23, pp. 9839–9849, 2018.

[4] V.S. Murthi, J. Dura, S. Satija, and C. Majkrzak, “Water Uptake and Interfacial Structural Changes of Thin Film Nafion Membranes Measured by Neutron Reflectometry for PEM Fuel Cells,” ECS Transactions, vol. 16, no. 2, 2019.

[5] D.L. Wood, J. Chlistunoff, J. Majewski, and R.L. Borup, “Nafion Structural Phenomena at Platinum and Carbon Interfaces,” Journal of the American Chemical Society, vol. 131, no. 50, pp. 18096–18104, 2009.

[6] C.R. Randall and S.C. DeCaluwe, “Physically Based Modeling of PEMFC Cathode Catalyst Layers: Effective Microstructure and Ionomer Structure–Property Relationship Impacts,” Journal of Electrochemical Energy Conversion and Storage, vol. 17, no. 4, Jan. 2020.