Regulating electrolytic Fe0.5CoNiCuZnx high entropy alloy electrodes for oxygen evolution reactions in alkaline solution

doi:10.1016/j.jmst.2021.03.046

Abstract

Abstract:

The properties of high entropy alloys (HEAs) depend on their phase structures and compositions. However, it is difficult to control the composition of the HEAs that contain highly volatile metals by the conventional arc melting method. In this paper, homogeneous powdery face centered cubic (FCC) phase Fe_0.5CoNiCuZn_x HEAs were prepared by the electrolysis of metal oxides in molten Na₂CO₃-K₂CO₃ using a stable Ni11Fe10Cu inert oxygen-evolution anode. The use of oxide precursors and relatively low synthetic temperature are beneficial to efficiently preparing HEAs that contain highly volatile elements such as Zn. Moreover, the microstructures and compositions of the electrolytic HEAs can be easily tailored by adjusting the components of oxide precursors, then further regulating its properties. Thus, the electrocatalytic activity of Fe_0.5CoNiCuZn_x HEAs towards oxygen evolution reactions (OER) was investigated in 1 M KOH. The results show that Zn promotes the OER activity of Fe_0.5CoNiCuZn_x HEAs, i.e., the HEA(Zn_0.8) shows the best OER activity exhibiting a low overpotential of 340 mV at 10 mA/cm² and excellent stability of 24 h. Hence, molten salt electrolysis not only provides a green approach to prepare Fe_0.5CoNiCuZn_x HEAs but also offers an effective way to regulate the structure of the alloys and thereby optimizes the electrocatalytic activities for water electrolysis.

Key words: High entropy alloy, Molten salt electrolysis, Zn-containing alloys, Water electrolysis, Oxygen evolution reaction

Jian Huang, Peilin Wang, Peng Li, Huayi Yin, Dihua Wang. Regulating electrolytic Fe_0.5CoNiCuZn_x high entropy alloy electrodes for oxygen evolution reactions in alkaline solution[J]. J. Mater. Sci. Technol., 2021, 93: 110-118.

Figures/Tables 8

Fig. 1. Schematic illustration of the molten-salt electrolytic preparation of Fe0.5CoNiCuZnx HEAs.

Fig. 2. (a) XRD patterns of the sintered oxide mixture and the reduced products after electrolysis at 1123 K and 2 V for 4 h. (b) Current?time curve of electrolysis at 2 V and 1123 K for 4 h. (c) SEM image of the sintered oxide mixture. (d) SEM image of the electrolytic product.

Fig. 3. EDS elemental mapping of the electrolytic products after electrolysis at 2 V and 1123 K for 4 h.

Fig. 4. (a) XRD patterns of the electrolytic products with different Zn contents at 1123 K and 2 V for 4 h. (b) The corresponding current-time plots. (c?f) SEM images of HEA(Zn0), HEA(Zn0.2), HEA(Zn0.5), and HEA(Zn0.8).

Fig. 5. XRD patterns of the pure metal mixture after electrolysis at 1123 K and 2 V for 4 h in molten Na2CO3-K2CO3.

Fig. 6. (a) LSV polarization curves of bulk Fe0.5CoNiCuZnx electrodes in 1 M KOH. (b) The corresponding Tafel slopes derived from (a). (c) Chronopotentiometry plots of different electrodes operated at 10 mA/cm2 for 24 h. (d) LSV polarization curves of the HEA(Zn0.8) electrode before and after chronopotentiometry test for 24 h at 10 mA/cm2.

Fig. 7. (a) LSV polarization curves of bulk electrodes Fe, Co, Ni, Cu and Zn in 1 M KOH. (b) Chronopotentiometry plots of bulk electrodes mentioned above operated at 10 mA/cm2 for 24 h.

Fig. 8. XPS spectra of Cu 2p (a and b), Ni 2p (c and d), Fe 2p (e and f), Co 2p (g and h), and Zn 2p (i and j) before and after OER performance of Fe0.5CoNiCuZnx HEAs electrodes, respectively.

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