Ti-V基固溶体/AB5型镧镁基合金复合储氢材料的结构与电化学性能

doi:10.3724/SP.J.1077.2012.00463

摘要/Abstract

摘要：

两步电弧熔炼法制备Ti_0.10Zr_0.15V_0.35Cr_0.10Ni_0.30 + 5wt% La_0.85Mg_0.25Ni_4.5Co_0.35Al_0.15复合储氢合金, X射线衍射(XRD)和扫描电镜-能谱(SEM-EDS)显示: 复合储氢合金的主相是体心立方结构的钒基固溶体相和六方结构的C14 Laves相, 复合过程中生成了第二相. 电化学研究表明: 复合过程中存在明显的协同效应; 在303 K时, 复合合金电极的实际最大放电容量为361.8 mAh/g; 在233 K时, 复合合金电极的低温放电能力(LTD)是母体合金电极的4.05倍. 与母体合金电极相比, 复合合金电极的高倍率放电性能(HRD)提高了26.87%, 电荷转移电阻(R_ct)减小了37.25 mΩ, 同时交换电流密度(I₀)增大了115.45 mA/g, 合金体内氢的扩散系数(D)增大了6.13×10^-10 cm²/s.

关键词: 钛钒基固溶体, 复合储氢合金, 电化学性能, 协同效应

Abstract:

Composite hydrogen storage alloy Ti_0.10Zr_0.15V_0.35Cr_0.10Ni_0.30 + 5wt% La_0.85Mg_0.25Ni_4.5Co_0.35Al_0.15 was prepared by two-step arc melting. X-ray diffractometry (XRD) and scanning electron microscope-energy dispersive spectroscopy (SEM-EDS) show that the main phase of the composite alloy consists of V-based solid solution phase with BCC structure and C14 Laves phase with hexagonal structure, while secondary phase also exists in the composite alloy. Electrochemical studies show that distinct synergetic effect appears during the composite process. The real maximum discharge capacity of the composite alloy electrode is 361.8 mAh/g at 303 K, and the low temperature dischargeability (LTD) of the composite alloy electrode is 4.05 times as high as that of the matrix alloy electrode at 233 K. The high rate dischargeability (HRD), the charge–transfer resistance (R_ct) and the exchange current density (I₀) of the composite alloy electrode are 26.87 % bigger, 37.25 mΩ lower and 115.45 mA/g higher than that of the matrix alloy electrode, respectively. The hydrogen diffusion coefficient (D) in the bulk of the composite alloy is 6.13×10^-10cm²/s bigger than that of the matrix alloy.

Key words: Ti-V-based solid solution, composite hydrogen storage alloy, electrochemical characteristics, synergetic effect

中图分类号:

O646
TG139

王艳芝, 赵敏寿. Ti-V基固溶体/AB₅型镧镁基合金复合储氢材料的结构与电化学性能[J]. 无机材料学报, 2012, 27(5): 463-468.

WANG Yan-Zhi, ZHAO Min-Shou. Structure and Electrochemical Characteristics of Ti-V-based Solid Solution/AB₅-type La-Mg-based Alloy Composite Hydrogen Storage Material[J]. Journal of Inorganic Materials, 2012, 27(5): 463-468.

图/表 11

图1 LMBA、TVS以及COM铸态合金的XRD图谱

Fig. 1 XRD patterns of LMBA, TVS and COM as-cast alloy

Table 1 Lattice parameters of BCC and C14 Laves phase in TVS and COM alloy

Sample	Phase	Lattice parameter		Cell volume /nm³
Sample	Phase	a / nm	c / nm	Cell volume /nm³
TVS alloy	BCC	0.2969	-	0.02617
TVS alloy	C14 Laves	0.4948	0.8093	0.17160
COM alloy	BCC	0.2974	-	0.02630
COM alloy	C14 Laves	0.4943	0.8069	0.17070

图2 表2 COM合金中各相的组成

Fig. 2 SEM images of COM alloy at different magnification

Table 2 Phase compositions of COM alloy

Phase	Composition / at%
Phase	Ti	Zr	V	Cr	Ni	Mg	Al	Co	La
BCC phase	4.95	10.04	38.03	14.86	7.39	12.02	10.08	2.62	－
C14 Laves phase	26.45	28.54	14.97	2.77	9.56	8.96	7.78	0.98	－
Secondary phase	1.22	29.80	31.54	6.34	9.94	7.49	6.39	1.18	6.10

图3 TVS和COM合金电极的电化学放氢P-C-T曲线

Fig. 3 Electrochemical desorption P-C-T curve of TVS and COM alloy electrode

图4 TVS、LMBA及COM合金电极的活化性能和最大放电容量

Fig. 4 Activation property and maximum discharge capacity of TVS, LMBA and COM alloy electrode

图5 表3 TVS和COM电极合金中主要元素在KOH 电解液中的溶出量

Fig. 5 Curve of discharge capacity vs cycle number for TVS and COM alloy electrode

Table 3 Concentration of main constituent element dissolved in KOH electrolyte for TVS and COM alloy electrode

Constituent element	Concentration in KOH / (mg·L^-1)
	50 cycles		100 cycles
	TVS	COM	TVS	COM
Ti	0.031	0.024	0.084	0.117
Zr	13.524	12.693	27.393	19.742
V	31.052	26.961	74.094	54.263
La	－	－	－	0.003
Mg	－	－	－	0.004

图6 温度对TVS和COM合金电极放电容量的影响

Fig. 6 Dependence of dischargeability on temperature for TVS and COM alloy electrode

图7 TVS和COM合金电极的高倍率放电性能

Fig. 7 High rate dischargeability of TVS and COM alloy electrode

图8 TVS和COM合金电极的EIS图谱

Fig. 8 Electrochemical impedance spectra of TVS and COM alloy electrode

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Ti-V基固溶体/AB₅型镧镁基合金复合储氢材料的结构与电化学性能

Structure and Electrochemical Characteristics of Ti-V-based Solid Solution/AB₅-type La-Mg-based Alloy Composite Hydrogen Storage Material

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