Activity and Stability of High-Surface-Area Nickel-Based Catalysts for the Alkaline Hydrogen Evolution Reaction Under Industrially Relevant Conditions
Authors: Feidenhans'l Anders A. , Egelund Sune Daaskov , Chorkendorff Ib , Kibsgaard Jakob , Larrazábal Gastón O. 
Published: February 2024

Alkaline water electrolysis (AWE) is at a stage of high technological maturity, and modern pressurized designs have mitigated the weaknesses of now-outdated atmospheric electrolyzers. For instance, pressurized systems now deliver high hydrogen outputs and can efficiently adjust to rapid changes in power loads. These improvements were, in part, made possible through significant reductions to internal ohmic losses coming from improved gas separators, shorter distances between electrodes, and increased operating temperatures.
From an industrial point of view, the critical parameter to optimize is the full stack voltage. The stack voltage is tightly bound to the individual cell voltage and can thus be lowered by employing more efficient electrocatalysts. However, reducing the cell voltage by raising the temperature of operation—thereby improving both reaction kinetics and the conductivity of the KOH electrolyte—can be of similar or even higher importance (e.g., ca. 4.5 mV/˚C, Figure 1) [1]. Therefore, stability under operation at elevated temperatures must be considered when evaluating novel hydrogen and oxygen evolution reaction catalysts for AWE. Else, a novel catalyst risks becoming the bottleneck in the pursuit of higher operating temperatures, limiting its applicability for large-scale electrolysis [2]. Many assessments of novel AWE catalysts are still carried out at room temperature in diluted electrolytes and at low current densities [3]. In the harsher conditions of an electrolyzer, catalysts experience higher dissolution rates and are subject to higher mechanical stress from, for instance, the aggressive bubble evolution. This gap hinders the transfer of catalyst developments from academia to industrial research laboratories and, ultimately, to practical applications.
In this work, we attempted to narrow that gap by conducting electrochemical measurements under more application-oriented conditions (i.e., 80-120 °C and 8-11 M KOH). We evaluated the HER activity and the robustness of high-surface-area electrodes produced through controlled leaching of bimetallic nickel-based alloys. A parametric study of the overpotential and robustness as a function of electrochemically active surface area was enabled by varying the synthesis parameters of a Raney-type preparation. Direct coupling to renewable energy sources requires the electrolyzer to frequently and rapidly shut off and on. This intermittent operation induces additional stress on the electrodes as the catalysts transition through different redox states, which is often overlooked in AWE electrocatalyst research. To track redox, compositional, and morphological changes, we used ex situ X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy. At the same time, the dissolution and redeposition of ionic species were monitored using inductively coupled plasma mass spectrometry. By matching the characterization data with the evolution of the overpotential until complete deactivation, we gained an understanding of the degradation mechanisms in high-surface-area nickel-based electrodes. These results shed light on the challenges and prospects of this promising class of electrocatalysts for alkaline HER under industrial conditions.
Acknowledgement:
This work is partly funded by the Innovation Fund Denmark (IFD) under File No. 1044-00162B.
References:
[1] Egelund, S. Development of low-cost heterogeneous electrocatalysts for large scale advanced alkaline electrolysers with focus on oxygen evolution and system performance. Ph.D. Dissertation, Technical University of Denmark: Kgs. Lyngby, Denmark, 2015.
[2] J. C. Ehlers, A. A. Feidenhans’l, K. T. Therkildsen, and G. O. Larrazábal, “Affordable Green Hydrogen from Alkaline Water Electrolysis: Key Research Needs from an Industrial Perspective,” ACS Energy Lett.
2023, 8, 3, 1502–1509.
[3] McCrory, C. C. L.; Jung, S.; Ferrer, I. M.; Chatman, S. M.; Peters, J. C.; Jaramillo, T. F. Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices. J. Am. Chem. Soc.
2015, 137 (13), 4347– 4357.

Figure 1