Structure and Electrochemical Hydrogen Storage Properties of as-Milled Mg-Ce-Ni-Al-Based Alloys

doi:10.1007/s40195-019-00990-4

Abstract

Abstract:

At room temperature, crystalline Mg-based alloys, including Mg₂Ni, MgNi, REMg₁₂ and La₂Mg₁₇, have been proved with weak electrochemical hydrogen storage performances. For improving their electrochemical property, the Mg is partially substituted by Ce in Mg-Ni-based alloys and the surface modification treatment is performed by mechanical coating Ni. Mechanical milling is utilized to synthesize the amorphous and nanocrystalline Mg_1-_xCe_xNi_0.9Al_0.1 (x = 0, 0.02, 0.04, 0.06, 0.08) + 50 wt%Ni hydrogen storage alloys. The effects made by Ce substitution and mechanical milling on the electrochemical hydrogen storage property and structure have been analyzed. It shows that the as-milled alloys electrochemically absorb and desorb hydrogen well at room temperature. The as-milled alloys, without any activation, can reach their maximal discharge capacities during first cycling. The maximal value of the 30-h-milled alloy depending on Ce content is 578.4 mAh/g, while that of the x = 0.08 alloy always grows when prolonging milling duration. The maximal discharge capacity augments from 337.4 to 521.2 mAh/g when milling duration grows from 5 to 30 h. The cycle stability grows with increasing Ce content and milling duration. Concretely, the S₁₀₀ value augments from 55 to 82% for the alloy milled for 30 h with Ce content rising from 0 to 0.08 and from 66 to 82% when milling the x = 0.08 alloy mechanically from 5 to 30 h. The alloys’ electrochemical dynamics parameters were measured as well which have maximum values depending on Ce content and keep growing up with milling duration extending.

Key words: Mg-Ni-based alloy, Ce substituting Mg, Surface modification, Mechanical milling, Electrochemical performance

Yanghuan Zhang, Zhenyang Li, Wei Zhang, Wengang Bu, Yan Qi, Shihai Guo. Structure and Electrochemical Hydrogen Storage Properties of as-Milled Mg-Ce-Ni-Al-Based Alloys[J]. Acta Metallurgica Sinica (English Letters), 2020, 33(5): 630-642.

Figures/Tables 14

Fig. 1 XRD profiles of sample alloys: a as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, b Ce0.08 alloy for different milled time

Fig. 2 SEM images and EDX curves of the as-cast Mg1-xCexNi0.9Al0.1 (x = 0-0.08) alloys: a-d SEM of Ce0, Ce0.04, Ce0.06 and Ce0.08 alloys, e-g EDX of Mg2Ni, Ni and Ce2Ni7

Fig. 3 HRTEM micrographs and ED patterns of the as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for different durations: a-c Ce0, Ce0.04 and Ce0.06 alloys milled for 10 h; d-f Ce0.08 alloy milled for 10 h, 20 h and 30 h

Fig. 4 Evolution of the discharge capacity of sample alloys: (a) as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, (b) Ce0.08 alloy for different milled times

Fig. 5 Evolution of the capacity retaining rates (Sn) of sample alloys: a as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, b Ce0.08 alloy for different milled time

Fig. 6 Evolution of the capacity retaining rates (Sn) of sample alloys: a as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, b Ce0.08 alloy for different milled times

Fig. 7 SEM images before and after electrochemical cycles and XRD curve after cycling of Ce0.08 alloy: a 5-h-milled Ce0.08 before cycling, b 5-h-milled Ce0.08 after cycling, c 30-h-milled Ce0.08 after cycling, d 30-h-milled Ce0.08 after cycling

Fig. 8 Discharge potential curves of sample alloys: a as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, b Ce0.08 alloy for different milled times

Fig. 9 Evolution of the HRD of sample alloys: a as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, b Ce0.08 alloy for different milled times

Fig. 10 Semilogarithmic curves of anodic current vs. time responses of sample alloys: a as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, b Ce0.08 alloy for different milled times

Fig. 11 Potentiodynamic polarization curves of sample alloys: a as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, b Ce0.08 alloy for different milled times

Fig. 12 Electrochemical impedance spectra (EIS) of the Ce0.08 alloy milled for different times and the equivalent circuit

Fig. 13 Electrochemical impedance spectra (EIS) of as-milled (30 h) Ce0.02 and Ce0.06 alloys at various temperatures: a Ce0.02 alloy, b Ce0.06 alloy

Fig. 14 Evolutions of the activation enthalpy ΔrH* values of sample alloys: a as-milled Mg1-xCexNi0.9Al0.1 (x = 0-0.08) + 50Ni alloys milled for 30 h, b Ce0.08 alloy for different milled times

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