Structural and Electrochemical Properties of A2B7-type La1-xScxNi2.6Co0.3Mn0.5Al0.1 (x = 0~0.5) Hydrogen Storage Alloys

doi:10.15541/jim20150125

Abstract

Abstract:

A₂B₇-type La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0-0.5) hydrogen storage alloys were prepared by vacuum arc melting method and annealed at 1173 K. XRD and SEM-EDS results showed that the annealed alloys mainly consisted of La₂Ni₇, LaNi₅, LaNi, and ScNi₂phases. The enthalpy of formation calculation analyses showed that the enthalpy of formation of binary alloy of Sc-Ni was more negative than that of La-Ni and Mg-Ni. This was one of the main reasons that the phase rule of Sc-contained alloy was different from Mg-contained alloy, which facilitated forming ScNi₂phase. The electrochemical measurement results showed that the discharge capacity and the cycle stability of the alloys were all firstly increased and then decreased with the x value increasing. The discharge capacity and cyclic stability (S₁₀₀) of alloy electrodes reached the maximum of 261.1 mAh/g and 80.47%, respectively, when x value was equal to 0.2. The appropriate amount of Sc in alloy could obviously inhibit the hydrogen-induced amorphous, meanwhile the alloy with Sc content also tends to form the non-hydrogen absorbing ScNi₂ phase, which is the main reason that the discharge capacity of alloy electrode is not significantly improved.

Key words: Re-Ni based A2B7-type hydrogen storage alloys, Sc element substitution, microstructure, electrochemical properties

CLC Number:

TG146

MEI Xing-Zhi, LUO Yong-Chun, ZHANG Guo-Qing, KANG Long. Structural and Electrochemical Properties of A₂B₇-type La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0~0.5) Hydrogen Storage Alloys[J]. Journal of Inorganic Materials, 2015, 30(10): 1049-1055.

Figures/Tables 11

Fig. 1 XRD patterns of the annealed alloys La1-xScxNi2.6Co0.3Mn0.5Al0.1 (a) and the alloys after hydrogenation (b)

Fig. 2 Phases abundance in the annealed alloys versus Sc content (x)

Fig. 3 Unit cell volume of the annealed alloys versus Sc content (x)

Fig. 4 SEM back scattered electron images of the annealed alloys. (a) x = 0; (b) x = 0.2; (c) x = 0.5 (α: LaNi5 phase, β: La2Ni7 phase, γ: LaNi phase, δ: ScNi2 phase)

Table 1 EDS analysis results of the phase areas of the annealed alloys

Sample	Phase area	Phase composition / at%						Stoichiometric B/A
Sample	Phase area	La	Sc	Ni	Co	Mn	Al	Stoichiometric B/A
x = 0	α area /LaNi₅ type	16.7	0	60.1	6.8	12.5	3.9	4.99
	β area /La₂Ni₇ type	22.1	0	60.9	5.6	9.6	1.8	3.52
	γ area /LaNi type	48.7	0	50.5	0.6	0.1	0.1	1.05
x = 0.2	α area /LaNi₅ type	16.3	0.2	60.2	6.6	12.9	3.6	5.06
	β area /La₂Ni₇ type	20.3	2.0	58.7	5.4	9.9	1.7	3.48
	γ area /LaNi type	49.0	0.2	49.9	0.6	0.1	0.2	1.03
	δ area /ScNi₂ type	0.9	31.9	47.0	10.3	8.7	1.2	2.05
x = 0.5	α area /LaNi₅ type	16.6	0.3	61.2	5.9	11.9	4.1	5.02
	β area /La₂Ni₇ type	20.0	2.2	62.4	4.5	8.1	2.8	3.50
	γ area /LaNi type	48.5	0.4	50.1	0.5	0.2	0.3	1.04
	δ area /ScNi₂ type	0.8	32.2	46.4	9.5	9.7	1.4	2.03

Fig. 5 Curves of the enthalpy formation for binary alloy Mg-Ni, La-Ni and Sc-Ni

Fig. 6 Curves of the enthalpy formation for ternary alloy La1-x(Mg, Sc)xNi3.5

Fig. 7 Activation curves of the alloy electrodes

Fig. 8 Discharge curves of the alloy electrodes after activation

Fig. 9 Cycle stability curves of alloy electrodes

Fig. 10 Discharge capacity and cycle life of the alloy electrodes as a function of Sc content(x)

References 25

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Structural and Electrochemical Properties of A₂B₇-type La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0~0.5) Hydrogen Storage Alloys

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