退火温度对无镁La-Y-Ni系A2B7型合金相结构和电化学性能的影响

doi:10.15541/jim20170222

摘要/Abstract

摘要：

用XRD、SEM、EDS和电化学测试方法研究了退火温度对A₂B₇型La_0.33Y_0.67Ni_3.25Mn_0.15Al_0.1储氢合金微观组织和电化学性能的影响规律。结果表明, 合金铸态组织由2H-Ce₂Ni₇、3R-Gd₂Co₇、CaCu₅和3R-Ce₅Co₁₉型相组成; 随退火温度(850~950℃)升高, Ce₂Ni₇型主相丰度和晶胞体积逐渐增加, 至950℃退火后, CaCu₅和Gd₂Co₇型相基本消失, 主相Ce₂Ni₇型相丰度和晶胞体积均达到最大值; 退火温度≥950℃时, Ce₂Ni₇型和Ce₅Co₁₉型相丰度分别又有所减少和增加。950℃退火合金具有较低的放氢平台压(1.92~8.70 kPa)和较高的电化学放电容量(371 mAh/g), 经100次充放电循环后其容量保持率S₁₀₀达到89%。退火合金电极的HRD性能均得到不同程度的提高, 其中950℃退火合金具有最佳的大电流放电性能(HRD₉₀₀=83.4%)。氢在合金中的扩散是影响其高倍率放电性能的控制因素。

关键词: 储氢合金, La-Y-Ni系电极材料, 热处理, 微观组织, 电化学性能

Abstract:

Effects of annealing temperature on the microstructure and electrochemical properties of A₂B₇-type La_0.33Y_0.67Ni_3.25Mn_0.15Al_0.1 hydrogen storage alloys were systematically investigated by XRD, SEM, EDS, and electrochemical measurements. Results showed that the alloy was composed of CaCu₅-type, 2H-Ce₂Ni₇-type, 3R-Gd₂Co₇-type and 3R-Ce₅Cu₁₉-type phases. Both abundance and unit cell volume of Ce₂Ni₇-type phase increased gradually with the anneale temperature increase when the annealing temperature was lower than 950℃. CaCu₅-type and Gd₂Co₇-type phases disappeared at 950℃, but both abundance and unit cell volume of the Ce₂Ni₇-type phase maximized. When annealing temperature was higher than 950℃, Ce₂Ni₇-type phase decreased while Ce₅Co₁₉type phase increased. The alloy, annealed at 950℃, had the lowest hydrogen desorption platform pressure (0.0192~0.087 atm), maximum hydrogen storage capacity (1.35wt%) and high electrochemical discharge capacity (371 mAh/g) with the maximum capacity retention S₁₀₀ at 89% after 100 cycle. The high rate discharge ability (HRD) of the annealed alloys were significantly improved, the alloy annealed at 950℃ had the best performance and HRD₉₀₀ was up to 83.4%. These well performances demonstrated that it is the hydrogen diffusion in the alloys that controls the high rate discharge.

Key words: hydrogen storage materials, La-Y-Ni-based electrode material, heat treatment, microstructure, electrochemical properties

中图分类号:

TG146
TG139

王浩, 罗永春, 邓安强, 赵磊, 姜婉婷. 退火温度对无镁La-Y-Ni系A₂B₇型合金相结构和电化学性能的影响[J]. 无机材料学报, 2018, 33(4): 434-440.

WANG Hao, LUO Yong-Chun, DENG An-Qiang, ZHAO Lei, JIANG Wan-Ting. Annealing Temperature on Structural and Electrochemical Property of Mg-free La-Y-Ni Based A₂B₇-type Hydrogen Storage Alloys[J]. Journal of Inorganic Materials, 2018, 33(4): 434-440.

图/表 12

图1 不同温度退火合金La0.33Y0.67Ni3.25Mn0.15Al0.1微观组织SEM背散射电子图像

Fig. 1 Backscattered SEM images of the La0.33Y0.67Ni3.25Mn0.15Al0.1 alloys annealed at different temperatures (a) As cast; (b) 850℃; (c) 900℃; (d) 950℃; (e) 1000℃; (f) 1050℃

表1 铸态合金成份及退火合金组织各物相微区元素组成的ICP及EDS分析结果

Table 1 Element compositions by ICP for the as-cast alloy and EDS results of the annealed alloys in phase regions

Alloy	Phase area	Atomic ratios of different elements/at%					Stoichiometric B/A
Alloy	Phase area	La	Y	Ni	Mn	Al	Stoichiometric B/A
As-cast (ICP) As-cast	CaCu₅-type	5.3	16.7	69.9	4.4	3.7	3.54
	CaCu₅-type	3.4	14.1	76.0	4.2	2.3	4.71
	Ce₂Ni₇(Gd₂Co₇)-type	4.6	15.0	74.4	3.8	2.2	3.42
	Ce₅Ni₁₉-type	3.8	15.4	74.5	3.7	3.0	4.08
850℃	CaCu₅-type	3.1	13.7	76.3	3.2	3.8	4.95
	Ce₂Ni₇(Gd₂Co₇)-type	5.0	15.5	73.8	3.4	3.3	3.41
	Ce₅Ni₁₉-type	4.0	15.7	73.6	3.7	3.0	4.08
900℃	CaCu₅-type	3.1	13.8	75.0	3.8	3.6	5.06
	Ce₂Ni₇(Gd₂Co₇)-type	5.5	16.2	71.4	3.7	2.5	3.58
	Ce₅Ni₁₉-type	4.3	16.1	72.1	3.5	3.4	3.76
950℃	Ce₂Ni₇-type	6.2	16.0	71.4	3.3	3.1	3.41
950℃	Ce₅Co₁₉-type	5.1	15.8	72.1	4.0	3.0	3.85
1000℃	Ce₂Ni₇-type	5.8	16.4	70.6	4.7	2.5	3.47
1000℃	Ce₅Co₁₉-type	4.8	15.9	71.4	4.9	3.3	3.90
1050℃	Ce₂Ni₇-type	5.2	16.5	72.0	4.5	2.6	3.51
1050℃	Ce₅Co₁₉-type	4.6	16.2	72.1	4.6	2.5	3.81

图2 不同温度退火时La0.33Y0.67Ni3.25Mn0.15Al0.1金的XRD (a), (b)和950℃退火合金XRD全谱拟合图谱(c)

Fig. 2 XRD patterns of La0.33Y0.67Ni3.25Mn0.15Al0.1 alloys annealed at different temperatures (a), (b) and Rietveld reﬁnement pattern of the alloy annealed at 950℃ (c)

图3 热处理温度对物相组成相丰度的影响

Fig. 3 Dependence of the phases abundance on annealing temperature

图4 热处理温度对物相晶胞体积的影响

Fig. 4 Correlation of cell volume of the phases with annealing temperature

图5 不同温度退火合金电极的充放电活化曲线

Fig. 5 Activation curves of the alloy electrodes annealed at different temperatures

图6 不同温度退火合金电化学放氢P-C-T曲线

Fig. 6 Electrochemical P-C desorption isotherms at 298 K of the alloy electrodes annealed at different temperatures

图7 不同温度退火合金电极的充放电循环曲线

Fig. 7 Discharge capacity versus the number of cycles for the alloy electrodes annealed at different temperatures

表2 不同温度退火La0.33Y0.67Ni3.25Mn0.15Al0.1合金电极的储氢和电化学性能

Table 2 Hydrogen storage and electrochemical properties of La0.33Y0.67Ni3.25Mn0.15Al0.1 alloy electrodes annealed at different temperatures

Alloy	N_a	C_max/(mAh•g^-1)		(H/M)/wt%	S₁₀₀/%	HRD₉₀₀/%	I₀/(mA•g^-1)	D₀/ (×10^-10, cm²•s^-1)	I_corr/(mA•g^-1)
Alloy	N_a	60/(mA•g^-1)	100/(mA•g^-1)	(H/M)/wt%	S₁₀₀/%	HRD₉₀₀/%	I₀/(mA•g^-1)	D₀/ (×10^-10, cm²•s^-1)	I_corr/(mA•g^-1)
As-cast	3	299.2	252.4	1.07	77.7	78.8	330.9	1.18	6.82
850℃	3	347.2	303.5	1.10	78.2	80.3	278.6	1.57	6.19
900℃	3	353.3	318.5	1.21	78.3	82.3	229.9	1.82	6.14
950℃	3	371.5	365.2	1.35	88.9	83.4	243.5	2.68	5.01
1000℃	5	370.4	358.6	1.34	86.5	80.6	269.1	2.56	5.12
1050℃	6	365.2	356.7	1.28	81.5	76.4	321.5	2.32	5.23

图8 不同温度退火合金电极的Tafel极化曲线

Fig. 8 Tafel polarization curves of the alloy electrodes annealed at different temperatures

图9 不同退火温度下合金电极的高倍率放电曲线

Fig. 9 High-rate discharge ability (HRD) at 298 K of the alloy electrodes at different annealing temperatures

图10 退火温度对合金电板交换电流密度I0和氢扩散系数D0的影响 3 结论

Fig. 10 Effect of annealing temperature on I0 and D0 for the alloy electrodes

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退火温度对无镁La-Y-Ni系A₂B₇型合金相结构和电化学性能的影响

Annealing Temperature on Structural and Electrochemical Property of Mg-free La-Y-Ni Based A₂B₇-type Hydrogen Storage Alloys

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