Hydrogen Storage Thermodynamics and Dynamics of Nd-Mg-Ni-Based NdMg12-Type Alloys Synthesized by Mechanical Milling

doi:10.1007/s40195-016-0423-0

Abstract

Abstract:

Nanocrystalline and amorphous NdMg₁₂-type NdMg₁₁Ni + x wt% Ni (x = 100, 200) hydrogen storage alloys were synthesized by mechanical milling. The effects of Ni content and milling time on hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The gaseous hydrogen absorption and desorption properties were investigated by Sieverts apparatus and differential scanning calorimeter connected with a H₂ detector. Results show that increasing Ni content significantly improves hydrogen absorption and desorption kinetics of the alloys. Furthermore, varying milling time has an obvious effect on the hydrogen storage properties of the alloys. Hydrogen absorption saturation ratio (\(R_{ 1 0}^{\text{a}}\); a ratio of the hydrogen absorption capacity in 10 min to the saturated hydrogen absorption capacity) of the alloys obtains the maximum value with varying milling time. Hydrogen desorption ratio (\(R_{ 2 0}^{\text{d}}\), a ratio of the hydrogen desorption capacity in 20 min to the saturated hydrogen absorption capacity) of the alloys always increases with extending milling time. The improved hydrogen desorption kinetics of the alloys are considered to be ascribed to the decreased hydrogen desorption activation energy caused by increasing Ni content and milling time.

Key words: NdMg12, alloy, Hydrogen, storage, Mechanical, milling, Activation, energy, Kinetics

Yang-Huan Zhang, Ze-Ming Yuan, Wen-Gang Bu, Feng Hu, Ying Cai, Dong-Liang Zhao. Hydrogen Storage Thermodynamics and Dynamics of Nd-Mg-Ni-Based NdMg₁₂-Type Alloys Synthesized by Mechanical Milling[J]. Acta Metallurgica Sinica (English Letters), 2016, 29(6): 577-586.

Figures/Tables 12

Fig. 1 XRD profiles of the as-cast and milled (10 h) NdMg11Ni + x wt% Ni (x = 0, 100, 200) alloys before and after hydriding. a Before, b after hydriding

Fig. 2 SEM images a together with typical EDS spectra b, c of the as-cast NdMg11Ni alloy

Fig. 3 HRTEM micrographs and ED patterns of the as-milled (10 h) NdMg11Ni + x wt% Ni (x = 100, 200) alloys. a, cx = 100, b, dx = 200

Fig. 4 P-C-T curves of the as-milled NdMg11Ni + x wt% Ni (x = 100, 200) alloys at 573 K. ax = 100, bx = 200

Fig. 5 P-C-T curves of the as-milled (10 h) NdMg11Ni + x wt% Ni (x = 100, 200) alloys in the temperature range of 553-613 K and Van’t Hoff diagrams. ax = 100, bx = 200

Table 1 Enthalpy and entropy changes of the as-milled alloys

NdMg₁₁Ni + x wt% Ni	Absorption		Desorption
NdMg₁₁Ni + x wt% Ni	ΔH (kJ/mol H₂)	ΔS (J/K/mol H₂)	ΔH (kJ/mol H₂)	ΔS (J/K/mol H₂)
x = 100	-69	-128	80	137
x = 200	-68	-126	74	129

Fig. 6 Hydrogen absorption kinetic curves of the as-milled NdMg11Ni + x wt% Ni (x = 100, 200) alloys at 573 K. ax = 100, bx = 200

Fig. 7 Evolutions of the values of the as-milled NdMg11Ni + x wt% Ni (x = 100, 200) alloys at 573 K alloys with milling time

Fig. 8 Hydrogen desorption kinetic curves of the as-milled (10 h) NdMg11Ni + x wt% Ni (x = 100, 200) alloys at 553, 573, 593 and 613 K. ax = 100, bx = 200

Fig. 9 Plots of ln[-ln(1-α)] versus ln t of the as-milled (10 h) NdMg11Ni + x wt% Ni (x = 100, 200) alloys at 553, 573, 593 and 613 K and Arrhenius plots. ax = 100, bx = 200 (4)

Fig. 10 DSC curves of the as-milled (10 h) NdMg11Ni + x wt% Ni (x = 100, 200) alloys at various heating rates and Kissinger plots. ax = 100, bx = 200

Fig. 11 Variations of hydrogen desorption activation energies of the as-milled NdMg11Ni + x wt% Ni (x = 100, 200) alloys calculated by Arrhenius and Kissinger methods with milling time

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Hydrogen Storage Thermodynamics and Dynamics of Nd-Mg-Ni-Based NdMg₁₂-Type Alloys Synthesized by Mechanical Milling

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