稀土系A2B7型La1-xScxNi2.6Co0.3Mn0.5Al0.1(x = 0~0.5)储氢合金相结构和电化学性能研究

doi:10.15541/jim20150125

摘要/Abstract

摘要：

真空电弧熔炼制备了A₂B₇型La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x=0~0.5)储氢合金并进行退火热处理。XRD及SEM/EDS分析结果表明, 合金退火组织由La₂Ni₇、LaNi₅、LaNi和ScNi₂等相组成。合金生成焓计算表明, Sc-Ni体系的生成焓比La-Ni和Mg-Ni体系的生成焓更负, 这是含Sc合金易于形成ScNi₂相以及成相规律有别于含Mg合金的主要原因之一。合金电极最大放电容量和循环寿命S₁₀₀随着Sc含量x增加均呈先增大后减小规律, 当x = 0.2时, 合金电极具有最大的放电容量(267.1 mAh/g)和较好的容量保持率S₁₀₀(80.47%)。掺入适量Sc元素后可抑制A₂B₇型合金的氢致非晶化, 但掺入Sc后合金易形成难吸氢的ScNi₂相, 这是合金电极容量不高的主要原因。

关键词: 稀土-镍系A2B7型储氢合金, 钪元素替代, 相结构, 电化学性能

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

中图分类号:

TG146

梅兴志, 罗永春, 张国庆, 康龙. 稀土系A₂B₇型La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0~0.5)储氢合金相结构和电化学性能研究[J]. 无机材料学报, 2015, 30(10): 1049-1055.

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.

图/表 11

图1 退火合金La1-xScxNi2.6Co0.3Mn0.5Al0.1(a)及其氢化后(b)的XRD图谱

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

图2 退火合金各物相丰度随Sc含量x的变化

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

图3 退火合金各物相晶胞体积随Sc含量x的变化

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

图4 退火合金微观组织的SEM背散射电子图像

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)

表1 退火合金各物相区元素组成EDS分析结果

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

图5 二元合金Mg-Ni、La-Ni和Sc-Ni生成焓曲线

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

图6 三元合金La1-x(Mg, Sc)xNi3.5生成焓曲线

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

图7 合金电极的活化曲线

Fig. 7 Activation curves of the alloy electrodes

图8 合金电极经活化后的放电曲线

Fig. 8 Discharge curves of the alloy electrodes after activation

图9 合金电极的充放电循环曲线

Fig. 9 Cycle stability curves of alloy electrodes

图10 合金电极放电容量和循环寿命与Sc含量x的关系

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

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稀土系A₂B₇型La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0~0.5)储氢合金相结构和电化学性能研究

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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