Which Insights Can Gas Diffusion Electrode Half-Cell Experiments Give into Activity Trends and Transport Phenomena of Membrane Electrode Assemblies?
Authors: Schmidt Mareike , Schmitt Nicolai , Jaschonek Katharina , Etzold Bastian J.M. 
Published: August 2024

In order to push the energy turnaround forward, research and development on technologies enabling storage and release of renewable energies, such as water electrolysis and fuel cells is vital in the current decade. For both processes it is essential to collect meaningful data for catalyst activity in terms of transferability to the industrial application already on the lab-scale and at an early stage of material development. Gas diffusion electrode (GDE) half-cell setups were recently presented as a fast and cost-effective tool to characterize oxygen reduction reaction (ORR) catalyst layers at fuel cell relevant potentials and current densities (3 A cm-2) [1]. An Inter-lab comparison demonstrated that GDE testing with various, slightly differing setups can deliver data that is both reliable and comparable if standardized measurement protocols are followed [2]. On the way to widespread application, it is essential to evaluate to which extend GDE half-cell measurements can provide reasonable trends of how catalyst layer properties influence ORR activity in membrane electrode assembly (MEA) applications, despite the major influence of the active metal itself. Elucidating possibilities and limitations of GDE half-cell measurements to study catalyst layer influences is scope of this study.
The transferability of trends was studied for i) an ionic liquid modified and unmodified Pt/C catalyst (following our previous work [3]) and ii) employing nitrogen modified carbon support at different ionomer to carbon ratios (following the work of Ott et al. [4]). Regarding the activity increase due to IL modification we will show that rotating disk electrode (RDE) and GDE results at low current densities show the same trend. GDE testing also shows a maximum activity depending on the IL loading at slightly elevated current densities. In the high current density regime, however, MEA testing showed a negative effect of the IL modification, which was also obtained correctly within the GDE testing at the same current densities. For the N-doped Pt/C catalyst a positive effect was observed in MEA characterization with low ionomer content under dry conditions, where proton transport losses are dominant for the unmodified catalyst. However, at higher I/C ratio and under wet conditions, where proton transport is sufficient for both unmodified and N-doped catalyst, worse performance after N modification is observed in the high current density regime. During GDE evaluation only the latter phenomenon could be capture and the unmodified catalyst showed a superior performance over the N-doped material at any I/C ratio in the ohmic and in the mass transport limiting regime.
In summary, we showed that GDE half-cell experiments, where the catalyst layer is in direct contact with the liquid electrolyte, can be used to reliably predict trends in catalytic activity for real MEAs at high current densities that are related to differences in oxygen mass transport [5]. However, differences in catalytic activity being related to proton accessibility especially at lower relative humidities cannot be captured completely, as the catalyst layer is always wetted fully. An introduction of an ionomer membrane between catalyst layer and liquid electrolyte might be necessary during GDE evaluation for a reliable description of all transport phenomena in real fuel cells. Nevertheless, our results indicate that GDE measurements without the utilization of an ionomer membrane allow for the study of oxygen mass transport properties independent of other transport phenomena at fuel cell relevant current densities.
Literature:
[1] Schmitt et al. Electrochemistry Communications
2022, 141, 107362 [2] Ehelebe et al. ACS Energy Lett.
2022, 7, 816-826. [3] Zhang et al. Advanced Functional Materials 31.28 (2021): 2010977 [4] Ott et al. Nature materials 19.1 (2020): 77-85. [5] Schmitt et al. Energy Adv.
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