(Invited) Highly Active OER Electrodes Derived from Fe-Doped Ni Oxyfluoride Formed by Anodizing of NiFe Electrodeposits

Abstract

Because of the limited availability of fossil fuels and pertinent global environmental issues, hydrogen production via electrochemical water splitting using renewable resources is an important alternative for future energy economies. For efficient alkaline water electrolysis to produce hydrogen, we need to develop highly active and durable electrocatalysts, particularly for oxygen evolution reaction (OER) because of high overpotential. Anodizing of metals and alloys is a promising means of directly fabricating an OER electrocatalyst on a metallic current collector. Binder-free electrocatalysts are readily formed by anodizing. Since Fe-doped Ni oxyhydroxides and hydroxides are recently reported as highly active OER electrocatalysts in alkaline media. Here, we report anodizing of NiFe electrodeposits in fluoride-containing ethylene glycol electrolyte and the conversion of resultant nanoporous Fe-doped Ni oxyfluoride to highly OER active hydroxide during OER (1).NiFe alloy films containing 7.2 – 21.1 at% Fe were obtained by electrodeposition on Ni substrate. Then, the alloys were anodized at 10 V in ethylene glycol electrolyte containing ammonium fluoride and water. The anodizing developed a porous layer consisting of crystalline NiF2 phase. XPS analysis revealed the presence of Fe and O as well as Ni and Fe. Thus, porous Fe-doped Ni oxyfluoride was developed by anodizing. The as-anodized NiFe alloys were initially less active for OER in 1.0 mol dm-3 KOH, but during potential cycling to OER potential, the OER activity was gradually enhanced. The enhancement was dependent upon Fe content, and the highest activity was obtained for the Ni-11.8 at% Fe. After activation, the porous layer was converted to amorphous hydroxide, and the fluoride content was highly reduced. Thus, anodically formed Fe-doped oxyfluoride on the NiFe electrodeposits is a suitable precursor of highly active OER electrocatalyst. The galvanostatic durability test exhibited the stable overpotential, disclosing the high durability of this electrocatalyst.Reference N. Yamada, S. Kitano, Y. Yato, D. Kowalski, Y. Aoki and H. Habazaki, ACS Applied Energy Materials, in press, doi.org/10.1021/acsaem.0c02362.