Phase transformation, thermodynamics and kinetics property of Mg90Ce5RE5 (RE = La, Ce, Nd) hydrogen storage alloys

doi:10.1016/j.jmst.2020.02.042

Abstract

Abstract:

The Mg₉₀Ce₅RE₅ (RE = La, Ce, Nd) alloys were prepared by a vacuum induction furnace and their microstructure, phase transformation, thermodynamics and kinetics property were systematically studied by XRD, SEM, TEM, and PCT characterization methods. The result shows that the activated alloys are composed of Mg/MgH₂ and corresponding REH₂₊_x with nanoscale. The REH₂₊_x grain with Ce and La or Nd functional group have lower nucleation potential barriers than CeH₂₊_x grains as the nucleation location, thus improve the hydrogen absorption kinetics of these alloys among which the Mg₉₀Ce₅Nd₅ alloy can absorb 90% of the hydrogen within 2 min at 320 oC. In addition, the Mg₉₀Ce₁₀ alloy has the lowest activation energy with 103.2 kJ mol ^-1 and the fastest desorption kinetics, which can release 5 wt% of the hydrogen within 20 min at 320 oC. This is a correlation with grain size and the in-suit formed CeH_2.73/CeO₂ interface. Moreover, the co-doping Ce and La or Nd can effectively disorganize the thermodynamic stability of Mg-based hydrogen storage alloys to a certain degree, but the dehydrogenation kinetics of that still is restricted by the recombination energy of hydrogen ions on the surface.

Key words: RE-Mg-based alloy, Hydrogen storage, Thermodynamics, Kinetics, Intermetallic

Hui Yong, Shihai Guo, Zeming Yuan, Yan Qi, Dongliang Zhao, Yanghuan Zhang. Phase transformation, thermodynamics and kinetics property of Mg₉₀Ce₅RE₅ (RE = La, Ce, Nd) hydrogen storage alloys[J]. J. Mater. Sci. Technol., 2020, 51: 84-93.

Figures/Tables 11

Table 1 Chemical compositions of Mg90Ce5RE5 (RE = La, Ce, Nd) alloys (at.%).

Alloy	Mg	Ce	RE	ΣRE
Mg₉₀Ce₅La₅	90.19	4.87	4.94	9.81
Mg₉₀Ce₁₀	90.27	9.73	-	.73
Mg₉₀Ce₅Nd₅	90.33	4.83	4.86	9.67

Fig. 1. XRD patterns of the as-cast Mg90Ce5RE5 (RE = La, Ce, Nd) alloys.

Fig. 2. SEM, HRTEM and SAED micrographs of the as-cast Mg90Ce5La5 (a, c) and Mg90Ce5Nd5 (b, d) alloys.

Fig. 3. XRD patterns of the alloys after hydrogenation (a) and dehydrogenation (b).

Fig. 4. TEM, SAED and HRTEM micrographs of the as-cast Mg90Ce5RE5 (RE = La, Ce, Nd) alloys after dehydriding: (a, b) La; (c, d) Ce; (e, f) Nd.

Fig. 5. PCT curves (a, c, e) of the activated Mg90Ce5RE5 (RE = La, Ce, Nd) alloys at different temperatures and the corresponding Van't Hoff graphs for La (a, b), Ce (c, d) and Nd (e, f).

Table 2 Platform pressure of hydrogen release and reversible hydrogen storage capacity of Mg90Ce5RE5 (RE = La, Ce, Nd) alloys.

Alloy	Equilibrium pressure (MPa)				C_max(wt%)
Alloy	380 °C	360 °C	340 °C	320 °C	C_max(wt%)
Mg₉₀Ce₅La₅	0.5322	0.3295	0.2006	0.1168	5.78
Mg₉₀Ce₁₀	0.5822	0.3608	0.2156	0.1229	5.74
Mg₉₀Ce₅Nd₅	0.3745	0.2342	0.1411	0.0823	5.65

Table 3 Enthalpy and entropy change of Mg90Ce5RE5 (RE = La, Ce, Nd) alloys.

Alloy	Hydrogen absorption		Hydrogen desorption
Alloy	ΔH (kJ mol^-1)	ΔS (J K^-1 mol^-1)	ΔH (kJ mol^-1)	ΔS (J K^-1 mol^-1)
Mg₉₀Ce₅La₅	-81.2	-138.2	82.9	140.7
Mg₉₀Ce₁₀	-82.9	-140.7	83.8	142.7
Mg₉₀Ce₅Nd₅	-81.4	-135.5	82.8	137.6

Fig. 6. Isothermal hydrogen absorption curves of Mg90Ce5RE5 (RE = La, Ce, Nd) alloys at various temperature for (a) La, (b) Ce, (c) Nd and (d) hydrogenation saturation ratio (R2min) as function of temperature.

Fig. 7. Isothermal hydrogen desorption curves of Mg90Ce5RE5 (RE = La, Ce, Nd) alloys at various temperature for (a) La, (b) Ce, (c) Nd and (d) hydrogen desorption curves of the alloys at 320 °C.

Fig. 8. JMAK plots of La (a), Ce (b), Nd (c) and Arrhenius plots (d) for the dehydrogenation Mg90Ce5RE5 (RE = La, Ce, Nd) alloys at different temperatures.

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Phase transformation, thermodynamics and kinetics property of Mg₉₀Ce₅RE₅ (RE = La, Ce, Nd) hydrogen storage alloys

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