Lattice mismatch in Ni3Al-based alloy for efficient oxygen evolution

doi:10.1016/j.jmst.2021.08.013

Abstract

Abstract:

The Ni₃Al-based alloy has been considered as a robust catalyst for oxygen evolution reaction (OER) due to its long-term durability and acceptable activity. However, related reports about understanding the catalytic mechanism are rare and desirable. Herein, the effect of γ/γ' phase lattice mismatch on the catalytic performance caused by various cooling rates after solution heat treatment was investigated. With decreasing cooling rate, the morphologies of γ′ precipitates transformed from sphere to cube and the lattice mismatch increased from -0.172% to -0.409%. The increased lattice mismatch facilitated the formation of the active β-NiOOH phase and enhanced the intrinsic catalytic activity, resulting in the optimized OER overpotential of 240 mV at a current density of 10 mA cm^-2 with a Tafel slope of 66.1 mV dec^-1 and a stability of 200 h in 1 M KOH. This work reveals the lattice mismatch effect on OER and provides a potential candidate for OER.

Key words: Ni₃Al alloy, γ′ precipitates, Annealing, Oxygen evolution electrocatalysts

Shicheng Li, Hongyan Liang, Chong Li, Yongchang Liu. Lattice mismatch in Ni₃Al-based alloy for efficient oxygen evolution[J]. J. Mater. Sci. Technol., 2022, 106: 19-27.

Figures/Tables 7

Fig. 1. SEM images of Ni3Al alloy after solution treatment at 1160 °C for 10 h with different cooling processes: (a) FC (0.05 °C/s), (b) AC (72 °C/s), and (c) WC (138 °C/s). (d) The averaged phase size and volume ratio of primary γ' phase of different cooling rates.

Fig. 2. (a) XRD results of WC, AC and FC specimens: an identification of γ′ and γ; γ/γ′ (200) deconvolution diffraction peak of FC (b), AC (c) and WC (d) using Pseudo-Voigt as fitting function.

Table 1. Lattice parameter (γ′ and γ) and lattice mismatch of Ni3Al alloy cooled by different cooling rates after solution treatment.

Cooling mode	2θ_γ′ (deg.)	α_γ′ (nm)	2θ_γ (deg.)	α_γ (nm)	Lattice mismatch, δ (%)
Furnace cooling	50.878 ± 0.002	0.358 ± 0.002	50.655 ± 0.003	0.360 ± 0.003	-0.409 ± 0.003
Air cooling	50.522 ± 0.001	0.361 ± 0.001	50.410 ± 0.002	0.362 ± 0.002	-0.206 ± 0.002
Water cooling	50.451 ± 0.001	0.361 ± 0.0001	50.359 ± 0.002	0.362 ± 0.002	-0.172 ± 0.002

Fig. 3. Primary γ' and γ channel of FC (a), AC (b) and WC (c) specimens observed by TEM. (d) HRTEM image of the region marked by red frame in (a); the inserted images show the FFT image of γ' and γ phases, respectively. (e) and (f) HRTEM images of the marked region in (b) and (c), respectively.

Fig. 4. Characterization of the electrochemical OER activities of Ni3Al electrodes. (a) LSV polarization curves with a scan rate of 2 mV/s. (b) The corresponding Tafel plots derived from LSV curves. (c) The relationship between overpotentials and lattice misfits (γ′ and γ) of different cooling rates. (d) Nyquist plots measured at open circuit potential by EIS. (e) LSV curves of FC specimen before and after 1000 CV cycles, and the multi-current process of FC specimens. The current density started at 5 mA cm-2 and finished at 50 mA cm-2, with an increment of 5 mA cm-2 per 1000 s. (f) Chronopotentiometry curve of FC specimens with a constant current density of 10 mA cm-2.

Fig. 5. XPS analysis of FC specimens before and after OER test: (a) Ni, (b)Al, (c) O, (d) Mo, (e) Cr and (f) Fe.

Fig. 6. (a) In-situ Raman spectra of the FC specimen under various applied potentials. (b) The magnification of (a). (c) In-situ Raman spectra of the FC, AC and WC specimen under 0.8 V (vs. Ag/AgCl) applied potentials.

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Lattice mismatch in Ni₃Al-based alloy for efficient oxygen evolution

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