Hydrogen Storage and Electrochemical Properties of the Mg-free A2B7-type La1-xYxNi3.25Mn0.15Al0.1 Alloys with Superlattice Structure†

doi:10.7503/cjcu20180169

Abstract

Abstract:

The new Mg-free A₂B₇-type La_1-_xY_xNi_3.25Mn_0.15Al_0.1(x=0—1.00) annealed alloys with superlattice structure were prepared by vacuum arc melting and heat treatment(950 ℃×10 h). The influences of Y element on the microstructure, hydrogen storage behavior and electrochemical performance of annealed alloys were investigated systematically. The results show that the main phase of all the annealed alloys is Ce₂Ni₇-type. With the increase of Y content, phase abundance of the Ce₂Ni₇-type phase increases firstly and then decreases, meanwhile the cell volumes decreases gradually. The x=0—0.25 alloys are easy to form hydrogen-induced amorphization(HIA), resulting in the disappearance of the plateau of pressure-composition-temperature(PCT) curves. When x≥0.50, the alloys can effectively avoid the HIA, the PCT curves obviously present an approximately single platform, the maximum hydrogen storage capacity and the plateau pressure of hydrogenation is in the range of 1.418%—1.48%(mass fraction) and 0.026—0.097 MPa, respectively. Therefore, the hydrogen storage performance has been greatly improved. The electrochemical measurement results show that the x=0.50—0.85 alloys exhibit the high discharge capacity of 350.4—381 mA·h/g and the cyclic stability of 52%—85% after 100 cycles, and the alloy with x=0.67—0.75 has good hydrogen storage and comprehensive electrochemical properties. The high rate discharge ability(HRD₉₀₀) of the alloys is 64.5%—85.7% and reaction kinetics of the electrode is mainly controlled by the diffusion rate of the hydrogen atom in body phase of the alloys.

Key words: A₂B₇-type La-Y-Ni based hydrogen storage alloy, Microstructure and phase structure, Hydrogen storage behavior, Electrochemical property

CLC Number:

O646
TG139.7

TrendMD:

ZHAO Lei,LUO Yongchun,DENG Anqiang,JIANG Wanting. Hydrogen Storage and Electrochemical Properties of the Mg-free A₂B₇-type La_1-_xY_xNi_3.25Mn_0.15Al_0.1 Alloys with Superlattice Structure^†[J]. Chem. J. Chinese Universities, 2018, 39(9): 1993.

Figures/Tables 15

Fig.1 Back scattered SEM images of the annealed La1-xYxNi3.25Mn0.15Al0.1(x=0—1) alloys (A) x=0; (B) x=0.25; (C) x=0.50; (D) x=0.67; (E) x=0.75; (F) x=0.85; (G) x=1.00.

Fig.2 EDS results for different regions of the annealed La1-xYxNi3.25Mn0.15Al0.1 alloys(x=0.5, 0.85) in Fig.1 (A) Area 1 of x=0.50; (B) area 2 of x=0.50; (C) area 3 of x=0.85; (D) area 4 of x=0.85.

Table 1 Chemical compositions of the annealed alloys La1-xYxNi3.25Mn0.15Al0.1 by ICP analysis

x	Normal composition	Chemical compositions by ICP, w(%)					Stoichiometric B/A ratio
x	Normal composition	La	Y	Ni	Mn	Al	Stoichiometric B/A ratio
0	LaNi_3.25Mn_0.15Al_0.1	40.80	0	54.42	3.14	1.64	3.52
0.25	La_0.75Y_0.25Ni_3.25Mn_0.15Al_0.1	31.01	6.48	58.67	2.93	0.91	3.56
0.50	La_0.5Y_0.5Ni_3.25Mn_0.15Al_0.1	21.67	14.10	60.53	2.66	0.94	3.54
0.67	La_0.33Y_0.67Ni_3.25Mn_0.15Al_0.1	14.49	19.35	62.74	2.56	0.87	3.56
0.75	La_0.25Y_0.75Ni_3.25Mn_0.15Al_0.1	10.84	22.35	63.34	2.54	0.92	3.45
0.85	La_0.15Y_0.85Ni_3.25Mn_0.15Al_0.1	6.28	25.70	64.66	2.41	0.94	3.53
1.00	YNi_3.25Mn_0.15Al_0.1	0	31.51	65.14	2.71	0.93	3.44

Fig.3 XRD patterns of the annealed La1-xYxNi3.25Mn0.15Al0.1(x=0—1.00) alloys(A, B) and Rietveld refinement XRD profile of the La0.15Y0.85Ni3.25Mn0.15Al0.1 alloy(C)

Table 2 Characteristics of phase structures and lattice parameters of the annealed alloys La1-xYxNi3.25Mn0.15Al0.1

x	Phase type	Space group	Lattice parameter							Phase abundance, w(%)
x	Phase type	Space group	a/nm	c/nm		c/a		V/nm³		Phase abundance, w(%)
0	Ce₂Ni₇-type	P63/mmc(194)	0.5060		2.4586		4.859		0.545154	39.56
	Gd₂Co₇-type	R $3 ˉ$ m(160)	0.5001		3.6326		7.264		0.786796	18.24
	Ce₅Co₁₉-type	R $3 ˉ$ m(160)	0.4952		4.9093		9.914		1.042585	17.64
	LaNi₅-type	P6/mmm(191)	0.5013		0.3987		0.795		0.086771	24.56
0.25	Ce₂Ni₇-type	P63/mmc(194)	0.5049		2.4521		4.857		0.541352	48.26
	Gd₂Co₇-type	R $3 ˉ$ m(160)	0.5000		3.6320		7.264		0.786351	10.38
	Ce₅Co₉-type	R $3 ˉ$ m(160)	0.4948		4.8743		9.851		1.033480	41.36
0.50	Ce₂Ni₇-type	P63/mmc(194)	0.5021		2.4393		4.858		0.532569	81.03
	PuNi₃-type	R $3 ˉ$ m(166)	0.5000		2.4350		4.870		0.527193	18.97
0.67	Ce₂Ni₇-type	P63/mmc(194)	0.5015		2.4332		4.852		0.530880	86.61
	PuNi₃-type	R $3 ˉ$ m(166)	0.5000		2.4350		4.870		0.529966	13.39
0.75	Ce₂Ni₇-type	P63/mmc(194)	0.5003		2.4303		4.858		0.526807	100.00
0.85	Ce₂Ni₇-type	P63/mmc(194)	0.4977		2.4223		4.867		0.519630	62.54
	YNi₃-type	R $3 ˉ$ m(166)	0.4986		2.4223		4.948		0.521511	37.46
1.00	Ce₂Ni₇-type	P63/mmc(194)	0.4965		2.4237		4.882		0.517426	56.72
	YNi₃-type	R $3 ˉ$ m(166)	0.4978		2.4361		4.894		0.522800	43.28

Table 2 Characteristics of phase structures and lattice parameters of the annealed alloys La1-xYxNi3.25Mn0.15Al0.1

x	Phase type	Space group	Lattice parameter							Phase abundance, w(%)
x	Phase type	Space group	a/nm	c/nm		c/a		V/nm³		Phase abundance, w(%)
0	Ce₂Ni₇-type	P63/mmc(194)	0.5060		2.4586		4.859		0.545154	39.56
	Gd₂Co₇-type	R $3 ˉ$ m(160)	0.5001		3.6326		7.264		0.786796	18.24
	Ce₅Co₁₉-type	R $3 ˉ$ m(160)	0.4952		4.9093		9.914		1.042585	17.64
	LaNi₅-type	P6/mmm(191)	0.5013		0.3987		0.795		0.086771	24.56
0.25	Ce₂Ni₇-type	P63/mmc(194)	0.5049		2.4521		4.857		0.541352	48.26
	Gd₂Co₇-type	R $3 ˉ$ m(160)	0.5000		3.6320		7.264		0.786351	10.38
	Ce₅Co₉-type	R $3 ˉ$ m(160)	0.4948		4.8743		9.851		1.033480	41.36
0.50	Ce₂Ni₇-type	P63/mmc(194)	0.5021		2.4393		4.858		0.532569	81.03
	PuNi₃-type	R $3 ˉ$ m(166)	0.5000		2.4350		4.870		0.527193	18.97
0.67	Ce₂Ni₇-type	P63/mmc(194)	0.5015		2.4332		4.852		0.530880	86.61
	PuNi₃-type	R $3 ˉ$ m(166)	0.5000		2.4350		4.870		0.529966	13.39
0.75	Ce₂Ni₇-type	P63/mmc(194)	0.5003		2.4303		4.858		0.526807	100.00
0.85	Ce₂Ni₇-type	P63/mmc(194)	0.4977		2.4223		4.867		0.519630	62.54
	YNi₃-type	R $3 ˉ$ m(166)	0.4986		2.4223		4.948		0.521511	37.46
1.00	Ce₂Ni₇-type	P63/mmc(194)	0.4965		2.4237		4.882		0.517426	56.72
	YNi₃-type	R $3 ˉ$ m(166)	0.4978		2.4361		4.894		0.522800	43.28

Fig.4 PCT curves of the La1-xYxNi3.25Mn0.15Al0.1 alloys at 300 K

Fig.5 Van’t Hoff plots for La1-xYxNi3.25Mn0.15Al0.1-H systems

Table 3 Hydriding absorption and hydrogen storage thermodynamic properties of the La1-xYxNi3.25Mn0.15Al0.1 alloys

x	Hydriding capacity at 8 MPa, w(%)		Plateau pressure/MPa		Hydrogen capacity at 8 MPa, w(%)	Hydrogen capacity at 0.1 MPa, w(%)	△H^0—/ (kJ·mol^-1 H₂)	△S^0—/(J· K^-1·mol^-1 H₂)	H_f	S_f
x	The 1st cycle	The 3rd cycle	Abs.	Des.	Hydrogen capacity at 8 MPa, w(%)	Hydrogen capacity at 0.1 MPa, w(%)	△H^0—/ (kJ·mol^-1 H₂)	△S^0—/(J· K^-1·mol^-1 H₂)	H_f	S_f
0	1.522	1.271	0.173	0.052	1.024	0.603	-38.26	96.29	0.52	3.66
0.25	1.485	1.119	0.218	0.037	0.983	0.573	-35.80	108.10	0.77	4.52
0.50	1.530	1.389	0.026	0.009	1.418	1.122	-34.25	77.22	0.46	1.10
0.67	1.442	1.444	0.054	0.031	1.425	1.128	-33.75	91.59	0.24	1.66
0.75	1.489	1.434	0.044	0.033	1.435	1.216	-34.19	78.11	0.12	0.88
0.85	1.528	1.513	0.094	0.046	1.490	0.804	-33.10	80.12	0.32	1.26
1.00	1.465	1.444	0.097	0.057	1.432	0.749	-32.91	79.21	0.22	1.59

Table 4 Electrochemical properties of La1-xYxNi3.25Mn0.15Al0.1 alloy electrodes

x	N_a	C_ma_x(mA·h/g)		S₁₀₀(%)	HRD₉₀₀(%)	I₀/ (mA·g^-1)	10¹⁰D₀/ (cm²·s^-1)	E_corr/V	i_corr/ (mA·cm^-2)
x	N_a	60 mA/g	300 mA/g	S₁₀₀(%)	HRD₉₀₀(%)	I₀/ (mA·g^-1)	10¹⁰D₀/ (cm²·s^-1)	E_corr/V	i_corr/ (mA·cm^-2)
0	2	211.3	152.3	92.1	64.5	321.8	0.91	-0.916	6.69
0.25	2	184.2	137.6	95.5	74.4	267.9	1.01	-0.919	6.57
0.50	1	376.1	340.6	75.6	75.6	249.0	1.32	-0.915	6.74
0.67	2	376.3	335.3	85.1	83.4	248.3	1.71	-0.912	5.81
0.75	1	381.6	347.2	80.3	85.7	274.3	2.56	-0.912	6.29
0.85	2	350.4	297.5	52.6	75.4	235.4	1.58	-0.927	8.75
1.00	1	307.2	164.1	22.1	68.1	51.9	0.94	-0.935	8.74

Fig.6 Correlation between the cell volume of Ce2Ni7 type phases and hydriding pressures in the PCT cueves

Fig.7 XRD patterns of the alloys before and after 50 hydrding/dehydrding cycles at 2 MPa

Fig.8 Activation and discharge potential curves of La1-xYxNi3.25Mn0.15Al0.1 alloy electrodes

Fig.9 Relationship between the discharge capacity and the solid-gas hydrogen absorption capacity at 0.1 MPa

Fig.10 Electrochemical cycling stability of the alloy electrodes

Fig.11 Tafel polarization curves of the alloy electrodes

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Hydrogen Storage and Electrochemical Properties of the Mg-free A₂B₇-type La_1-_xY_xNi_3.25Mn_0.15Al_0.1 Alloys with Superlattice Structure^†

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