A2B7型La0.3Y0.7Ni3.4-xMnxAl0.1储氢合金微观结构和电化学性能研究

doi:10.15541/jim20190190

摘要/Abstract

摘要：

采用真空电弧熔炼和均匀化退火制备La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1(x=0~0.5)储氢合金, 采用不同方法系统研究了Mn元素对合金微观结构、储氢和电化学性能的影响规律和作用。结果表明, 退火合金微观组织与Mn含量关系密切, 提高Mn含量有利于合金组织形成Ce₂Ni₇型相, 当x≥0.3时, 合金形成Ce₂Ni₇型结构单相组织。随Mn含量增加, Ce₂Ni₇型主相晶胞参数a、c及晶胞体积V均依次增大, 导致合金吸氢平台压从0.079 MPa降至0.017 MPa, 储氢量达到1.268wt%~1.367wt%。添加Mn元素能显著改善合金的电化学性能, x=0.1的合金电极的放电容量最高(390.4 mAh·g ^-1); x=0.15和0.5的合金电极的容量保持率S₁₀₀分别为86.1%和88.5%, 具有较好的循环稳定性。上述合金电极的高倍率放电性能HRD₉₀₀为71.53%~87.73%。分析结果表明, 合金电极反应动力学过程由电极/溶液界面的电子转移与体相中的氢原子扩散共同控制。

关键词: La-Y-Ni系合金, Mn元素替代, 储氢, 电化学性能

Abstract:

La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1(x=0-0.5) hydrogen storage alloys were prepared by vacuum arc melting followed by homogenized annealing. Effect of Mn element on the microstructure, hydrogen storage behavior and electrochemical properties were systematically investigated via different methods. The results show that the microstructure of the annealed alloys closely relates to the Mn content. Higher Mn content facilitates the formation of Ce₂Ni₇ type phase until single phase structure of Ce₂Ni₇- type forms in the alloys with x≥0.3. With the increment of Mn content, the unit cell parameters (a, c) and unit cell volume (V) of Ce₂Ni₇- type phase increase, resulting in the hydrogen absorption platform pressure of the alloys decreasing from 0.079 MPa to 0.017 MPa and the hydrogen storage capacities reaching 1.268wt%-1.367wt%. The electrochemical properties are significantly improved with the addition of Mn. La_0.3Y_0.7Ni_3.25Mn_0.15Al_0.1 alloy exhibits the highest discharge capacity (390.4 mAh·g ^-1). The capacity retention S₁₀₀ of the alloys with x=0.15 and 0.5 are 86.03% and 88.01%, respectively, presenting good cycle stability. Meanwhile, high rate discharge ability (HRD₉₀₀) of the as-prepared alloys is 71.53%-87.73%. It is shown that electrochemical reaction kinetics of the alloy electrodes is controlled by both the electron transfer at the electrode/ solution interface and the diffusion of hydrogen atoms in the alloy bulk.

Key words: La-Y-Ni based alloys, Mn substitution, hydrogen storage, electrochemical property

中图分类号:

TQ174

郑坤, 罗永春, 邓安强, 杨洋, 张海民. A₂B₇型La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1储氢合金微观结构和电化学性能研究[J]. 无机材料学报, 2020, 35(5): 549-555.

ZHENG Kun, LUO Yongchun, DENG Anqiang, YANG Yang, ZHANG Haiming. Microstructure and Electrochemical Property of A₂B₇-type La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1Hydrogen Storage Alloys[J]. Journal of Inorganic Materials, 2020, 35(5): 549-555.

图/表 15

表1 退火合金中各元素含量ICP分析结果

Table 1 Elements content of the annealed alloys by ICP analysis

Alloy	Element/wt%					Stoichiometric B/A ratio
Alloy	La	Y	Ni	Mn	Al	Stoichiometric B/A ratio
x=0	6.73	15.33	75.75	0.00	2.19	3.53
x=0.15	6.82	15.56	72.38	2.90	2.34	3.47
x=0.2	6.86	15.47	71.57	3.86	2.24	3.48
x=0.3	6.91	15.71	68.61	6.41	2.37	3.42
x=0.5	6.94	15.77	65.02	10.11	2.17	3.40

图1 退火合金微观组织SEM照片(a~e)及图(c)区域3中A2B7型相的EDS能谱分析(f)

Fig. 1 SEM images of the annealed alloys (a-e) and EDS pattern of A2B7-type phase in area 3 (a)x=0; (b)x=0.15; (c)x=0.2; (d)x=0.3; (e)x=0.5; (f) EDS pattern of A2B7-type phase in area 3 of fig.(c)

图2 退火合金的XRD图谱(a)、局部放大图(b)及x=0.15试样的Rietveld全谱拟合图(c)

Fig. 2 XRD patterns (a) and local enlarge XRD patterns (b) of the annealed alloys (a, b) and Rietveld refinement XRD profile of the sample x=0.15(c)

图3 退火合金的物相组成及各物相丰度

Fig. 3 Phase structure and phase abundances of the annealed alloys

图4 退火合金中Ce2Ni7型主相的晶胞参数(a, c)、轴比c/a和(插图)晶胞体积V

Fig. 4 Lattice parameters (a, c), c/a ratio and (insert)cell volume, V of Ce2Ni7 type phase for the annealed alloys

图5 退火合金的吸放氢PCT曲线(300 K)以及(插图)吸氢平台压, 晶胞体积与Mn含量的关系曲线

Fig. 5 PCT curves and (insert) the relationships between plateau pressure, cell volume and Mn content of the alloys at 300 K

图6 退火合金吸氢平衡时的lnPeq -1/T曲线

Fig. 6 lnPeq -1/T plots of the annealed alloys

图7 合金电极的充放电活化及(插图)电位曲线

Fig. 7 Activation and (insert) discharge potential curves of the alloy electrodes

图8 合金电极的充放电循环曲线及(插图)S100、放电容量与Mn含量的关系曲线

Fig. 8 Electrochemical cycling curves and (insert) the relationshipsbetween S100, discharge capacity and Mn content of the alloy electrodes

图9 合金电极经100次循环后的XRD图谱

Fig. 9 XRD patterns of the alloy electrodes after 100 electrochemical cycles

图10 合金电极经100次循环后表面形貌的SEM照片

Fig. 10 SEM images of the alloy electrodes after 100 electrochemical cycles

图11 经100次电化学循环后合金电极表面的XPS全谱(a)及其La3d(b)和Y3d(c)高分辨谱图

Fig. 11 Total XPS spectrum (a) and high resolution La3d(b) and Y3d(c) XPS spectra of the alloy electrodes after 100 electrochemical cycles

图12 合金电极的Tafel腐蚀极化曲线以及(插图)Ecorr、Icorr与Mn含量的关系曲线

Fig. 12 Tafel polarization curves and (insert) the relationshipsbetween Ecorr, Icorr and Mn content of the alloy electrodes

图13 合金电极的高倍率放电性能

Fig.13 High rate discharge ability of the alloy electrodes

图14 I0、D0与Mn含量x的关系曲线

Fig. 14 Relationships between I0, D0 and Mn content x

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A₂B₇型La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1储氢合金微观结构和电化学性能研究

Microstructure and Electrochemical Property of A₂B₇-type La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1Hydrogen Storage Alloys

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