Confocal Raman Microscopy – Shedding Light on the Ionomer Properties of PFSA Membranes
Authors: Maier Maximilian , Abbas Dunia , Komma Miriam , Solihul Mu'min Muhammad , Thiele Simon , Boehm Thomas 
Published: August 2024

Perfluorinated sulfonic acid (PFSA) polymers are the state-of-the-art material for the proton exchange membrane (PEM) in various electrochemical energy conversion devices, e.g., PEM fuel cells, PEM water electrolyzers, or redox flow batteries, combining chemical and mechanical durability with high proton conductivity.
The most prominent example of a PFSA material is NafionTM, which is a so-called long side chain (LSC) ionomer due to its comparably long side chain between the polymer backbone and the charged sulfonyl end group. On the other hand, short side chain (SSC) ionomers like Aquivion® and 3M Ionomer or composite membranes are promising approaches to improve performance in harsh conditions, such as low humidity or high operating temperatures.1 SSC PEMs feature increased water uptake, proton conductivity,2 and crystallinity3 compared to LSC PEMs. Composite PEMs can be specifically tailored to the required operating conditions by carefully designing the interlayers or additives. As the performance and longevity of electrochemical cells are a delicate convolution of various (composite) membrane properties and parameters, a method for evaluating ionomer membrane properties is crucial for rationally engineering optimized PEMs.
Here, we use confocal Raman microscopy (CRM) to investigate application-relevant properties of PFSA PEMs and for high-resolution imaging of composite membranes.4 Thus, the high spatial resolution of confocal optical microscopy and the chemical sensitivity of Raman scattering are combined in a single measurement approach. NafionTM, 3M Ionomer, and Aquivion® at varying equivalent weights (EW) feature distinctive Raman spectra (Fig. 1) that show characteristic spectral changes depending on the ionomer’s side chain structure and EW. We show that the EW of these PFSA types can be reliably measured using Raman spectroscopy. Further, parameters such as swelling, ionizable group content, and water uptake can be quantified by CRM non-destructively and contact-free. The diffraction-limited resolution of CRM of less than 2 µm enables a view of the local distribution of these properties and, therefore, allows to image and analyze composite membranes. In summary, we comprehensively study ionomer properties of (composite) membranes and establish CRM as a powerful platform for characterizing advanced PEMs for electrochemical energy device
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Figure 1