Effect of Y, Al Co-Doping on Hydrogen Storage Properties of La-Mg-Ni-Based Alloys

doi:10.1007/s40195-024-01709-w

Abstract

Abstract:

La-Mg-Ni-based hydrogen storage alloys have excellent hydrogen storage properties. This work reports the hydrogen storage performance of a series of A₂B₇-type La_0.96Mg_0.04Ni_3.34Al_0.13 alloy and La_0.96-_xY_xMg_0.04Ni_3.47-0.6_xAl_0.6_x (x = 0, 0.22, 0.33, 0.44) alloys, and explores the effect of Y and Al element combined substitution on the microstructure and hydrogen storage performance of A₂B₇-type La-Mg-Ni-based alloys. The alloys are composed of Ce₂Ni₇ phase and LaNi₅ phase. With the increase of x, the cell volume of Ce₂Ni₇ phase decreases, while that of LaNi₅ phase increases, indicating that Y atom mainly enters Ce₂Ni₇ phase and Al atom mainly enters LaNi₅ phase. An appropriate amount of co-substitution increases the hydrogen storage capacity and reduces the hydrogen absorption/desorption plateau pressure hysteresis of the alloy. When x = 0.44, the hydrogen storage capacity of the alloy is 1.449 wt%, and the hysteresis coefficient is 0.302. The cell volume of Ce₂Ni₇ phase and LaNi₅ phase expands to different degrees after 20 absorption/desorption cycles. With the increase of x, the volume expansion rate decreases, and the cycle capacity retention rate also gradually decreases. This is related to the amorphization of Ce₂Ni₇ phase. When x = 0.22, the capacity retention rate of the alloy is 91.4%.

Key words: La-Mg-Ni-based alloys, Gas-phase hydrogen storage performance, Ce₂Ni₇ phase, LaNi₅ phase, Capacity retention rate

Guanjiu Wu, Yichao Xie, Yuan Li, Qing Wang, Chenfeng Fan, Wenfeng Wang, Lu Zhang, Shumin Han. Effect of Y, Al Co-Doping on Hydrogen Storage Properties of La-Mg-Ni-Based Alloys[J]. Acta Metallurgica Sinica (English Letters), 2024, 37(8): 1399-1410.

Figures/Tables 17

References 40

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Design composition	La (wt%)	Y (wt%)	Mg (wt%)	Ni (wt%)	Al (wt%)	B/A	Actual composition
La_0.74Y_0.22Mg_0.04 Ni_3.34Al_0.13	31.89	6.09	0.27	60.68	1.06	3.47	La_0.74Y_0.22Mg_0.04 Ni_3.34Al_0.13
La_0.63Y_0.33Mg_0.04 Ni_3.27Al_0.20	27.68	9.37	0.30	61.02	1.63	3.47	La_0.63Y_0.33Mg_0.04 Ni_3.28Al_0.19
La_0.52Y_0.44Mg_0.04 Ni_3.21Al_0.26	23.41	12.67	0.35	61.27	2.3	3.47	La_0.52Y_0.44Mg_0.04 Ni_3.21Al_0.26

Design composition	La (wt%)	Y (wt%)	Mg (wt%)	Ni (wt%)	Al (wt%)	B/A	Actual composition
La_0.74Y_0.22Mg_0.04 Ni_3.34Al_0.13	31.89	6.09	0.27	60.68	1.06	3.47	La_0.74Y_0.22Mg_0.04 Ni_3.34Al_0.13
La_0.63Y_0.33Mg_0.04 Ni_3.27Al_0.20	27.68	9.37	0.30	61.02	1.63	3.47	La_0.63Y_0.33Mg_0.04 Ni_3.28Al_0.19
La_0.52Y_0.44Mg_0.04 Ni_3.21Al_0.26	23.41	12.67	0.35	61.27	2.3	3.47	La_0.52Y_0.44Mg_0.04 Ni_3.21Al_0.26

Alloy	Phase	Space group	a (Å)	c (Å)	V (Å³)	c/a	Phase abundance (wt%)
#1	Ce₂Ni₇	P63/mmc(194)	5.0502	24.6077	543.52	4.87	100
x = 0	Ce₂Ni₇	P63/mmc(194)	5.0433	24.5394	540.54	4.87	100
x = 0.22	Ce₂Ni₇	P63/mmc(194)	4.9722	24.5936	526.56	4.94	63
x = 0.22	LaNi₅	P6/mmm(191)	5.0058	3.9786	86.26	0.79	37
x = 0.33	Ce₂Ni₇	P63/mmc(194)	4.9744	24.5414	525.92	4.93	83
x = 0.33	LaNi₅	P6/mmm(191)	5.0051	3.9827	86.54	0.80	17
x = 0.44	Ce₂Ni₇	P63/mmc(194)	4.9636	24.5612	524.12	4.95	87
x = 0.44	LaNi₅	P6/mmm(191)	5.0101	3.9980	86.77	0.80	13

Alloy	Phase	Space group	a (Å)	c (Å)	V (Å³)	c/a	Phase abundance (wt%)
#1	Ce₂Ni₇	P63/mmc(194)	5.0502	24.6077	543.52	4.87	100
x = 0	Ce₂Ni₇	P63/mmc(194)	5.0433	24.5394	540.54	4.87	100
x = 0.22	Ce₂Ni₇	P63/mmc(194)	4.9722	24.5936	526.56	4.94	63
x = 0.22	LaNi₅	P6/mmm(191)	5.0058	3.9786	86.26	0.79	37
x = 0.33	Ce₂Ni₇	P63/mmc(194)	4.9744	24.5414	525.92	4.93	83
x = 0.33	LaNi₅	P6/mmm(191)	5.0051	3.9827	86.54	0.80	17
x = 0.44	Ce₂Ni₇	P63/mmc(194)	4.9636	24.5612	524.12	4.95	87
x = 0.44	LaNi₅	P6/mmm(191)	5.0101	3.9980	86.77	0.80	13

Alloy	Temperature (K)	Hydrogen content (wt%)	P_ab	P_de	H_f	ΔH_ab (kJ·mol⁻¹)	ΔH_de (kJ·mol⁻¹)
#1	303	0.986	Amor	Amor	-	-	-
	323	0.932	Amor	Amor	-
	348	1.013	Amor	Amor	-
x = 0	303	0.903	Amor	Amor	-	-	-
	323	0.879	Amor	Amor	-
	348	0.896	Amor	Amor	-
x = 0.22	303	1.352	0.281	0.187	0.407	− 27.101	25.239
	323	1.390	0.522	0.328	0.465
	348	1.340	1.128	0.682	0.503
x = 0.33	303	1.381	0.226	0.155	0.377	− 28.285	26.306
	323	1.368	0.448	0.294	0.421
	348	1.363	0.965	0.598	0.478
x = 0.44	303	1.449	0.188	0.139	0.302	− 29.216	27.572
	323	1.446	0.397	0.285	0.331
	348	1.443	0.843	0.573	0.386