无镁超点阵结构A2B7型La1-xYxNi3.25Mn0.15Al0.1合金的储氢和电化学性能

doi:10.7503/cjcu20180169

摘要/Abstract

摘要：

采用真空电弧熔炼和热处理(950 ℃×10 h)方法制备了新型无镁超点阵结构A₂B₇型La_1-_xY_xNi_3.25Mn_0.15Al_0.1(x=0, 0.25, 0.50, 0.67, 0.75, 0.85, 1.00)退火合金, 研究了A端稀土Y元素对退火合金微观组织结构、储氢行为及电化学性能的影响. 结果表明, 退火合金微观组织的主相均由Ce₂Ni₇型结构组成, 随稀土Y含量x增大, Ce₂Ni₇型主相丰度呈先增加后减小的规律, 同时Ce₂Ni₇型主相的晶胞体积V逐渐减小. 气体储氢时, x=0~0.25合金无压力-组成-温度(PCT)曲线平台且易形成氢致非晶化; 当x≥0.50时, 合金能有效抑制储氢时的氢致非晶化倾向且具有明显的吸/放氢平台特征, 吸氢平台压范围为0.026~0.097 MPa, 最大储氢量为1.418%~1.48%(质量分数), 储氢性能得到极大改善. 电化学测试结果表明, x=0.50~0.85的合金具有较高的电化学放电容量(350.4~381 mA·h/g), 经100次充放电循环后容量保持率S₁₀₀=52%~85%, 其中稀土Y含量x=0.67~0.75时的合金具有良好的储氢性能及较好的综合电化学性能. 合金电极的高倍率放电性能HRD₉₀₀=64.5%~85.7%, 氢原子在合金体相中的扩散是电极反应动力学过程的控制步骤.

关键词: La-Y-Ni系A₂B₇型储氢合金, 微观组织与相结构, 气体储氢行为, 电化学性能

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

中图分类号:

O646
TG139.7

TrendMD:

赵磊, 罗永春, 邓安强, 姜婉婷. 无镁超点阵结构A₂B₇型La_1-_xY_xNi_3.25Mn_0.15Al_0.1合金的储氢和电化学性能. 高等学校化学学报, 2018, 39(9): 1993.

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^†. Chem. J. Chinese Universities, 2018, 39(9): 1993.

图/表 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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无镁超点阵结构A₂B₇型La_1-_xY_xNi_3.25Mn_0.15Al_0.1合金的储氢和电化学性能

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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