The Effect of Water Quality on PEM Electrolyzer Performance
Authors: Rodriguez Mayra , Ravichandran Santosh , Sharan Prashant , Currier Robert P. , Findikoglu Alp Tugrul 
Published: August 2024

There has been growing interest in the use of removable, clean, and sustainable energy sources as a solution to eliminate environmental problems caused by fossil fuels. In particular, the electrolysis of water to produce green hydrogen is one of the most promising technologies. Among various electrolysis techniques, proton exchange membrane water electrolyzer (PEMWE) stands out as the most promising for mobility and large-scale energy-storage applications (1). Hydrogen production by PEMWEs requires approximately 45 kg of high-quality water to produce 5 kg of hydrogen. It has been estimated that about 22% of the total cost of a state-of-the-art PEMWE system is for water deionization treatment (2). This water purity requirement is not only an economic barrier, but also a constraint for the use of this system in areas where high-quality water is not accessible or in areas where water for human consumption is a scarce resource. Therefore, studying the effect of water quality on PEMWE performance is an important first step in identifying key degradation mechanisms on the path to discovering new PEMWE architectures that are more tolerant of poor-quality feed waters.
In this work, the effect of common impurities, such as Na+ and Mg2+, in feed water on the performance of common PEMWE architectures is studied. The main goals of the work are: 1) to understand the tolerance range for long term operation, 2) to identify major degradation mechanisms when the failure occurs. Experiments were carried out in an electrolyzer equipped with platinized Ti electrodes, IrO2 and Pt/C as anodic and cathodic catalysts, respectively, and a 115 Nafion® membrane. Durability studies of 100-hour duration and electrochemical characterization of the electrolyzer at different time intervals (polarization curves and impedance spectroscopy) were performed. The membrane/electrode assembly was probed by SEM /EDX before and after the experiments and cation concentrations in the water were monitored by ICP. An electrochemical model is proposed to explain the observed behavior of the electrolyzer with DI water and in the presence of impurities.
The results show that the presence of cations affects the performance of the electrolyzer at different levels depending on the concentration of the cation and its valence (Mg2+ > Na+ >DI water). Mg+2 had the same effect as Na+ even at 5 times lower concentration. Cations have higher affinity than protons for sulfonic acid groups (-SO3
-), leading to a displacement of protons and a consequent reduction in the membrane proton conductivity. However. according to the polarization curves, there are effects beyond the ohmic potential due to the increase in membrane resistance. The major effect of cations is on the reaction kinetics, which is the primary reason for the observed increase in cell voltage. The presence of cations within the membrane blocks the transport of protons, which creates a lack of protons at the cathode, resulting in the kinetic change from proton reduction to reduction of water. Moreover, the EDX results showed that Na+ and Mg2+ ions transfer from anode to cathode and deposit on the membrane and catalyst layers, which may cover the active catalyst sites, block the proton transport inside the membrane and degrade the catalyst ionomer layers.
References

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Becker H, Murawski J, Shinde DV, Stephens IEL, Hinds G, Smith G. Impact of impurities on water electrolysis: A review. Sustainable Energy & Fuels. 2023;7(7):1565-603.