Evaluation of Nickel-Iron (Oxy)Hydroxide Catalysts in Varied Electrode Geometries Under Industrially Realistic Conditions for Enhanced Alkaline Water Electrolysis

Abstract

In pursuit of realizing a hydrogen-based economy, the challenge lies in enhancing the efficiency of crucial water electrolysis technologies. Alkaline water electrolysis (AWE) holds promise as an ecologically friendly method for H2 production, primarily due to its capacity for employing non-precious metals as electrocatalysts, in contrast to more costly options which can only switch to noble metals such as ruthenium or iridium. However, this technology faces a significant challenge arising from the sluggish kinetics of the oxygen evolution reaction (OER), which constrains the overall efficiency. [1] Furthermore, the limited stability of many OER catalysts alternatives developed at lab scale and less harsh conditions poses a substantial obstacle to the commercialization of this technology.[2] To overcome this issue, the development of highly active OER catalysts that maintain their activity under industrial conditions is of major importance explaining the growing attention that this topic is gaining in literature. Nevertheless, most of the reported systems are tested at low current densities under easily manageable conditions in the laboratory (≤ 100 mA cm-2, 1 M KOH, RT). Without disagreeing that this approach is necessary to identify promising options among the numerous catalyst systems, it is not sufficient when competing with existing technologies that already achieve high current densities. In this context, we investigate a low-cost, abundantly available non-precious metal based OER-catalyst under industrially relevant conditions (≤ 1.2 A cm-2, 30 wt.-% KOH, 80 °C). The synthesis is based on a multistep galvanic deposition method introduced by Wu et al [3], receiving a highly porous NiFeOOH catalyst. Addressing the complexity of the multiphase process of AWE that involves gas-liquid-solid interfaces, the catalyst system is transferred to numerous nickel electrodes with different 3D geometries (plain woven mesh, knitted mesh, expanded metal mesh) for the investigation of their impact on bubble formation and detachment. To further optimize the catalyst system a variation of the iron content with respect to its’ molar fraction relatively to nickel has been carried out from x(Fe)=0 to x(Fe)=0.75, which after synthesis were first examined using SEM and EDS. The structure can be considered as pompom-shaped particles, forming a porous framework, as can be seen exemplarily in Figure 1a) on a knitted nickel-wire mesh coated with NiFeOOH. Observing variations in iron content, it becomes evident that a higher iron content results in larger particle sizes, thereby altering pore sizes. However, the surface morphologies of each catalyst until a molar fraction x(Fe)=0.5 is reached, can be considered as very similar. When comparing the SEM images of the mesh with a molar fraction x(Fe)=0.75 to the other molar fractions, a secondary phase becomes apparent on the surface. Notably, the porous structure persists within the crystalline phase. It could be shown by EDS that the target values for the molar fractions set in the galvanic bath and the actual molar fractions nearly show no deviations. Further, a uniform dispersion of Ni, Fe and O is observed.The electrochemical investigation of the prepared catalysts was done in a 3-electrode PTFE beaker cell setup in 30 wt % KOH and at 80 °C. The measurement protocol we introduce consists of galvanostatic steps between 0-1.2 A cm-2. The stability is tested chronopotentiometrically as well by maintaining a current density of 500 mA cm-2 for 100 h. It becomes apparent that no optimum is reached in the tested range of iron content and that the potential continues to drop as the molar fraction of Fe increases, achieving the lowest potential with 1.38 V vs. RHE at 50 mA cm-2 and 1.42 V vs. RHE at 750 mA cm-2 with x(Fe)=0.75. It could be further proved that the NiFeOOH catalyst with x(Fe)=0.75 is a highly stable catalyst, resulting in a potential increase of 27 mV over 100 h of testing at 500 mA cm-2, making it to an appropriate OER catalyst for the application in the AWE. The highly porous structure is maintained after testing, proved by SEM imaging. The iron contents after testing are also very similar, which means that there is almost no iron loss in the coating. For the different tested electrode geometries coated with NiFeOOH (x(Fe)=0.5), similar activity is observed, shown in Figure 1b) with a ranging potential between 1.38 V to 1.41 V vs. RHE at 50 mA cm-2 and 1.42 V to 1.45 V vs. RHE at 750 mA cm-2.[1] a) Cao et al., Energy Environ. Sci. 2012 b) Zhao et al., ACS Chemical Reviews 2023.[2] Zeng et al., Journal of Energy Chemistry 2022.[3] Wu et al., Applied Surface Science 2021. Figure 1