Electrode Coating Process Impact on the Performance of Pt and PtCo Fuel Cell Cathode Catalysts
Authors: Halim El Mahdi , Pierinet Lisa , Blanchard Rémi , Manikandan Maidhily , Tran Thi bich hue , Barker Micah , Kariyawasam Janith , Tricot Fanny , Durst Julien 
Published: February 2024

The polymer electrolyte membrane fuel cell (PEMFC) is one of the most promising energy sources for replacing fossil fuels in vehicles, as it does not produce greenhouse gas emissions during operation. As a key player in hydrogen mobility, SYMBIO is developing and producing PEMFC systems for a large field of applications. SYMBIO masters the electrochemical core (the Membrane Electrode Assembly - MEA), the complete stack (bipolar plate, stacking and housing) and the fuel cell system (Balance of Plant, operating conditions, control-command, packaging) [1].
The widespread use of fuel cell vehicles is strongly linked to the price of the PEMFC system, in which the MEA as a high share. Decreasing the total PGM content, as well as moving to high-speed roll-to-roll production methods are important levers in the cost roadmap of MEAs. And from a performance point of view, systems for the heavy-duty market will need to show high efficiencies at low current densities (<1 A/cm2). Exploring the potential of highly active cathode catalyst is therefore mandatory for these applications.
State of the art cathode catalyst layers consists in either Pt or PtCo-alloy supported on carbon material, the latter being more active for the ORR but also less resistant towards potential cycling. Regarding the ink formulation, the use of PtCo poses the challenge that Co atoms could dissolve, even if the catalyst has been previously acid leached, leading to the release of free Co2
+. These free ions will latter lower the catalytic activity and the transport of reactants (H+ and O2) to the active sites in the catalytic layer [2-3].
The manufacturing of a catalyst coated membrane (CCM) can be done with different printing processes involving a catalytic ink and a substrate. Each coating process has different constraints (ink rheological behaviour, particle size) leading to optimisation of ink recipe (solvent matrix, solid content ...). The ink must also be compatible with the substrate that can be directly an MEA component such as the membrane (direct coating) or the GDL, or a decal-carrier substrate. All these parameters lead to catalyst layer structure differences that impact the MEA performance.
In this study, the impact of three coating processes, hence three solvent systems for a same catalyst, ionomer, and I/C ratio, on the MEA performance is explored for commercial Pt and PtCo catalysts. The coating processes compared are direct coating on membrane via bar coater and spray coater and non-direct coating using decal method.
The inks properties including the granulometry and the viscosity of different prepared inks were characterized before coating. Ex-situ techniques (SEM-EDX, TEM, N2 adsorption/desorption) were used to figure-out the impact of the coating process on the morphology and porosity of the cathodic catalyst layer. The influence of these parameters on the electrochemical performance was studied using H2-Air polarization curves, electrochemical impedance spectroscopy and the electrochemical surface area (ECSA).
It will be highlighted how important the final PEMFC performance must be understood by taking into account the used ink system and coating process, as well as the intrinsic stability of catalyst, ionomer and membrane during these stages.

References

[1] www.symbio.one
[2] Nagappan Ramaswamy et al 2021 J. Electrochem. Soc. 168 024519
[3] Deborah J. Myers et al 2021 J. Electrochem. Soc. 168 044510