Microstructure and Electrochemical Property of A2B7-type La0.3Y0.7Ni3.4-xMnxAl0.1 Hydrogen Storage Alloys

doi:10.15541/jim20190190

Abstract

Abstract:

La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1(x=0-0.5) hydrogen storage alloys were prepared by vacuum arc melting followed by homogenized annealing. Effect of Mn element on the microstructure, hydrogen storage behavior and electrochemical properties were systematically investigated via different methods. The results show that the microstructure of the annealed alloys closely relates to the Mn content. Higher Mn content facilitates the formation of Ce₂Ni₇ type phase until single phase structure of Ce₂Ni₇- type forms in the alloys with x≥0.3. With the increment of Mn content, the unit cell parameters (a, c) and unit cell volume (V) of Ce₂Ni₇- type phase increase, resulting in the hydrogen absorption platform pressure of the alloys decreasing from 0.079 MPa to 0.017 MPa and the hydrogen storage capacities reaching 1.268wt%-1.367wt%. The electrochemical properties are significantly improved with the addition of Mn. La_0.3Y_0.7Ni_3.25Mn_0.15Al_0.1 alloy exhibits the highest discharge capacity (390.4 mAh·g ^-1). The capacity retention S₁₀₀ of the alloys with x=0.15 and 0.5 are 86.03% and 88.01%, respectively, presenting good cycle stability. Meanwhile, high rate discharge ability (HRD₉₀₀) of the as-prepared alloys is 71.53%-87.73%. It is shown that electrochemical reaction kinetics of the alloy electrodes is controlled by both the electron transfer at the electrode/ solution interface and the diffusion of hydrogen atoms in the alloy bulk.

Key words: La-Y-Ni based alloys, Mn substitution, hydrogen storage, electrochemical property

CLC Number:

TQ174

ZHENG Kun, LUO Yongchun, DENG Anqiang, YANG Yang, ZHANG Haiming. Microstructure and Electrochemical Property of A₂B₇-type La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1Hydrogen Storage Alloys[J]. Journal of Inorganic Materials, 2020, 35(5): 549-555.

Figures/Tables 15

Table 1 Elements content of the annealed alloys by ICP analysis

Alloy	Element/wt%					Stoichiometric B/A ratio
Alloy	La	Y	Ni	Mn	Al	Stoichiometric B/A ratio
x=0	6.73	15.33	75.75	0.00	2.19	3.53
x=0.15	6.82	15.56	72.38	2.90	2.34	3.47
x=0.2	6.86	15.47	71.57	3.86	2.24	3.48
x=0.3	6.91	15.71	68.61	6.41	2.37	3.42
x=0.5	6.94	15.77	65.02	10.11	2.17	3.40

Fig. 1 SEM images of the annealed alloys (a-e) and EDS pattern of A2B7-type phase in area 3 (a)x=0; (b)x=0.15; (c)x=0.2; (d)x=0.3; (e)x=0.5; (f) EDS pattern of A2B7-type phase in area 3 of fig.(c)

Fig. 2 XRD patterns (a) and local enlarge XRD patterns (b) of the annealed alloys (a, b) and Rietveld refinement XRD profile of the sample x=0.15(c)

Fig. 3 Phase structure and phase abundances of the annealed alloys

Fig. 4 Lattice parameters (a, c), c/a ratio and (insert)cell volume, V of Ce2Ni7 type phase for the annealed alloys

Fig. 5 PCT curves and (insert) the relationships between plateau pressure, cell volume and Mn content of the alloys at 300 K

Fig. 6 lnPeq -1/T plots of the annealed alloys

Fig. 7 Activation and (insert) discharge potential curves of the alloy electrodes

Fig. 8 Electrochemical cycling curves and (insert) the relationshipsbetween S100, discharge capacity and Mn content of the alloy electrodes

Fig. 9 XRD patterns of the alloy electrodes after 100 electrochemical cycles

Fig. 10 SEM images of the alloy electrodes after 100 electrochemical cycles

Fig. 11 Total XPS spectrum (a) and high resolution La3d(b) and Y3d(c) XPS spectra of the alloy electrodes after 100 electrochemical cycles

Fig. 12 Tafel polarization curves and (insert) the relationshipsbetween Ecorr, Icorr and Mn content of the alloy electrodes

Fig.13 High rate discharge ability of the alloy electrodes

Fig. 14 Relationships between I0, D0 and Mn content x

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Microstructure and Electrochemical Property of A₂B₇-type La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1Hydrogen Storage Alloys

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