Effects of Ni Content and Ball Milling Time on the Hydrogen Storage Thermodynamics and Kinetics Performances of La-Mg-Ni Ternary Alloys

doi:10.1007/s40195-019-00879-2

Abstract

Abstract:

The effects of Ni content and ball milling time on the hydrogen storage thermodynamics and kinetics performances of as-milled \({\text{La}}_{5} {\text{Mg}}_{95 - x} {\text{Ni}}_{x} \left( {x = 5, \, 10, \, 15} \right)\) ternary alloys have been investigated. The evolution of microstructure and phase of experimental alloys in the absorption/desorption process has been characterized by XRD, SEM and HRTEM. The hydrogen storage kinetics and thermodynamics performances and PCI curves have been tested using the Sievert apparatus. It is found that the rising of Ni content remarkably improves the hydrogen storage kinetic performance, but reduces hydrogen storage capacity. And with the increase in milling time, hydrogen desorption activation (E_a) value decreases firstly and then increases; the minimum value is 47.6 kJ/mol, and the corresponding milling time is 10 h for La₅Mg₈₅Ni₁₀ alloy. As for the thermodynamics properties, the hydrogenation enthalpy (ΔH) and hydrogenation entropy (ΔS) both decrease firstly and then increase with the rising of Ni content and milling time. The composite La₅Mg₈₅Ni₁₀ alloy milled for 10 h exhibits the best thermodynamics and kinetics performances, the lowest E_a of 47.6 kJ/mol, absorption of 5.4 wt.% within 5 min and desorption of 5.2 wt.% within 3 min at 360 °C and the lowest ΔH and ΔS of 72.1 kJ/mol and 123.2 J/mol/K.

Key words: Hydrogen storage, Mg-based alloys, Thermodynamics and kinetics, Ni content, Milling time

Zhen-Yang Li, Sheng-Li Li, Ze-Ming Yuan, Yang-Huan Zhang. Effects of Ni Content and Ball Milling Time on the Hydrogen Storage Thermodynamics and Kinetics Performances of La-Mg-Ni Ternary Alloys[J]. Acta Metallurgica Sinica (English Letters), 2019, 32(8): 961-971.

Figures/Tables 9

Fig. 1 XRD profiles of as-milled \({\text{La}}_{5} {\text{Mg}}_{95 - x} {\text{Ni}}_{x} \left( {x = 5, \, 10, \, 15} \right)\) alloys: a Ni5, Ni10, Ni15 alloys milled for 5 h; b Ni10 alloys with different milling times

Fig. 2 SEM images of Ni10 alloys: a, b as-cast Ni10 alloy; c, d Ni10 alloy milled for 10 h

Fig. 3 HRTEM micrographs and ED patterns of the as-milled Ni10 alloys with different milling times: a 5 h; b 10 h; c 20 h; d 30 h

Fig. 4 Hydrogen absorption kinetic curves of as-milled \({\text{La}}_{5} {\text{Mg}}_{95 - x} {\text{Ni}}_{x} \left( {x = 5, \, 10, \, 15} \right)\) alloys: a, b Ni5, Ni10, Ni15 alloys milled for 5 h at 360 °C and 100°C; c, d Ni10 alloys with different milling times at 360 °C and 100 °C

Fig. 5 Hydrogen desorption kinetic curves of as-milled \({\text{La}}_{5} {\text{Mg}}_{95 - x} {\text{Ni}}_{x} \left( {x = 5, \, 10, \, 15} \right)\) alloys: a, b Ni5, Ni10, Ni15 alloys milled for 5 h at 360 °C and 280 °C; c, d Ni10 alloys with different milling times at 360 °C and 280 °C

Fig. 6 Evolutions of the \(R_{*}^{{}}\) and \(R_{*}^{\text{d}}\) values of the as-milled \({\text{La}}_{5} {\text{Mg}}_{95 - x} {\text{Ni}}_{x} \left( {x = 5, \, 10, \, 15} \right)\) alloys: a Ni5, Ni10, Ni15 alloys milled for 5 h at 360 °C and 100 °C; b Ni10 alloys with different milling times at 360 °C and 100 °C; c Ni5, Ni10, Ni15 alloys milled for 5 h at 360 °C and 280 °C; d Ni10 alloys with different milling times at 360 °C and 280 °C

Fig. 7 JMA plots of ln[-?ln(1-α)] versus lnt and Arrhenius plots of as-milled \({\text{La}}_{5} {\text{Mg}}_{95 - x} {\text{Ni}}_{x} \left( {x = 5, \, 10, \, 15} \right)\) alloys: a Ni10 alloy milled for 5 h; b Ni5, Ni10, Ni15 alloys milled for 5 h; c Ni10 alloy milled for 20 h; d Ni10 alloys with different milling times

Fig. 8 P-C-I curves of the as-milled \({\text{La}}_{5} {\text{Mg}}_{95 - x} {\text{Ni}}_{x} \left( {x = 5, \, 10, \, 15} \right)\) alloys: a Ni5, Ni10, Ni15 alloys milled for 5 h at 360 °C; b Ni10 alloy milled for 5 h; c Ni10 alloys with different milling times at 360 °C; d Ni10 alloy milled for 20 h

Fig. 9 Variations of the ΔH and ΔS absolute values of the hydrogen desorption reactions of as-milled \({\text{La}}_{5} {\text{Mg}}_{95 - x} {\text{Ni}}_{x} \left( {x = 5, \, 10, \, 15} \right)\) alloys: a Ni5, Ni10, Ni15 alloys milled for 5 h; b Ni10 alloys with different milling times

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