The Effect of Cation Contamination on the Water Transport for PEM Water Electrolysis
Authors: Oezaslan Mehtap , Friedrichs-Schucht Maurice , Heine Nico , Hasché Frédéric 
Published: August 2024

Large-scale hydrogen production by PEM water electrolysis (PEMWE) in the energy sector requires a deep understanding of the system behaviour in failure cases and possible recovery procedures. This includes the purification of the anolyte feed water because the contamination with ions can cause the PEMWE stack to breakdown.[1] For instance, the presence of iron trace cations or other metal cations in the feed water leads to a performance loss due to higher ohmic resistance of the cell and higher iR-free voltages.[2]
[3] Moreover, cation contamination might influence the water transport in a PEMWE cell. In principle, the transfer of the water molecules to the cathode is proportional to the proton flux from the cathode to the anode. The proportionality factor is defined as water transport coefficient and is also temperature dependent.[4] In case of the mono- and multivalent cations as trace elements in the feed water, the water loading of the membrane, which is expressed by water molecules per sulfonic acid group of the membrane, λ, decreases over time and leads to successive increase in the ohmic resistance. [5] However, the influence of cation contamination on the water transport in PEMWE is poorly understood to date.
In this work, we investigated the effect of cation contamination in the anode feed water on the water crossover for PEMWE. Cation contamination experiments were carried out at a constant current density by adding different concentrations such as K2SO4, Na2SO4, etc. to the anode feed water. All electrochemical measurements were carried out in an in-house test bench equipped with a single cell of 5 cm2 geometric electrode area and potentiostat with booster. A commercially available catalyst coated perfluorosulfonic acid membranes (loading of 0.3 mg cm-2
geo Pt/C and 1 mgcm-2
geo IrOx) was used. The anode and cathode compartments were kept at atmospheric pressure and cell temperature of 80°C. To determine the water crossover from anode to cathode at different current densities, the cathode exhaust was cooled in a heat exchanger and measured by a gravimetric method. [4]

Firstly, a conditioning procedure was performed with purified feed water until steady cell performance was achieved. The cell performance was evaluated using polarization curves, electrochemical impedance spectroscopy (EIS) and water crossover measurements. The last two are of particular interest, because they provide information about membrane humidification. The Tafel slope and mass transport overvoltage were established from the polarization curves and high frequency resistance (HFR). We observed a significant rise of the cell voltage by adding cations to the anode water feed within few hours. The analysis of Tafel slope and EIS data also reveal an increase of ohmic and mass transport resistances. In these experiments, we were able to correlate the HFR results with the water crossover as a function of the nature of the cation and its concentrations. Our data shows that the specific water crossover per current density decreases as a consequence of cation contamination. The switch back to purified feed water allows us to monitor the dynamics of the performance recovery process obtained from EIS and water crossover measurements. Additional measurements of the polarization curves and HFR were used to distinguish between reversible and irreversible degradation processes due to the cation contamination.
Altogether, we present the effect of cation contamination on the water transport processes and provide deeper insights into the mass transport and performance losses for PEMWE.
References
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2016, 75, 395.
[2] C. Immerz, M. Singer, F. Hasché, B. Bensmann, M. Suermann, R. Hanke-Rauschenbach, M. Oezaslan 2020, MA2020-02, 2456.
[3] H. Becker, J. Murawski, D. V. Shinde, I. E. L. Stephens, G. Hinds, G. Smith, Sustainable Energy Fuels
2023, 7, 1565.
[4] M. Friedrichs-Schucht, F. Hasché, M. Oezaslan, ECS Trans.
2023, 111, 3.
[5] T. Okada, Y. Ayato, M. Yuasa, I. Sekine, J. Phys. Chem. B
1999, 103, 3315.