Coating Titanium Transport Layers for Enhanced Short and Long Term Performance in PEM Water Electrolysis Cells
Authors: Stein Lukas , Ismael Mohammed , Bensmann Boris , Hanke-Rauschenbach Richard , Dittrich Arne , Walter Dominic 
Published: August 2024

The ageing of titanium porous transport layers (PTL) affects the longevity of polymer electrolyte membrane water electrolysis systems by the formation and thickening of a weakly conductive oxide layer. The evolving oxygen on the anode in combination with the high electrical potential provides a challenging environment in which a low electrical contact resistance to the catalyst layer (CL) needs to sustain over a long period. One previous approach is a precious metal coating of the PTL with platinum or iridium [1], which can prevent oxidation of the titanium. A cost-effective alternative is a hydrochloric acid treatment, which forms titanium hydride (TiH). [2] Titanium nitride (TiN) promises better electrical conductivity with similar corrosion resistance, but has not yet been tested as a coating. The same is true for niobium, which performed well as a coating for stainless steel bipolar plates. [3] In our studies, all these candidates face the same conditions aside an untreated PTL in one unique series of measurements. All types are repeated three times to ensure reproducibility. The mean polarization curves (figure 1 left) show that the two precious metals, iridium and platinum, significantly improve the cell voltage at a current density of 2A/cm² by 80mV and 95mV, respectively. Titanium hydride achieves an even higher reduction of 100mV without the use of precious metals. The high frequency resistance plots in figure 1 right determine that the improvement of up to 20% or 30mΩ∙cm² is attributable to a reduced contact resistance to the CL. This assumption is proven by the fact that a PTL that is only coated with iridium on the side facing the CL behaves identically to a PTL that is coated on both sides. The ohmic losses in contact with the BPP are therefore negligible in these experiments. Titanium nitride and niobium coated PTLs behave in the same way as the reference measurement. In addition to the measurements shown, long-term experiments (>1000 hours) are currently running for all types of coating, and corrosion measurements in sulphuric acid are being carried out in parallel. The joint results will determine the suitability of the various coatings for long-term use in electrolysers.
[1] Liu, C., Shviro, M., Gago, A. S., Zaccarine, S. F., Bender, G., Gazdzicki, P., Morawietz, T., Biswas, I., Rasinski, M., Everwand, A., Schierholz, R., Pfeilsticker, J., Müller, M., Lopes, P. P., Eichel, R.-A., Pivovar, B., Pylypenko, S., Friedrich, K. A., Lehnert, W., Carmo, M., Exploring the Interface of Skin-Layered Titanium Fibers for Electrochemical Water Splitting. Adv. Energy Mater. 2021, 11, 2002926. https://doi.org/10.1002/aenm.202002926
[2] Bystron, T., Vesely, M., Paidar, M. et al. Enhancing PEM water electrolysis efficiency by reducing the extent of Ti gas diffusion layer passivation. J Appl Electrochem
48, 713–723 (2018). https://doi.org/10.1007/s10800-018-1174-6
[3] Stiber, S., Hehemann, M., Carmo, M., Müller, M., Ayers, K.E., Capuano, C., Danilovic, N., Morawietz, T., Biswas, I., Gazdzicki, P., Heger, J.-F., Gago, A.S. and Friedrich, K.A. (2022), Long-Term Operation of Nb-Coated Stainless Steel Bipolar Plates for Proton Exchange Membrane Water Electrolyzers. Adv. Energy Sustainability Res., 3: 2200024. https://doi.org/10.1002/aesr.202200024

Figure 1