Ti0.7Zr0.3(Cr1-xVx)2合金的结构和贮氢性能*

doi:10.3724/SP.J.1037.2013.00637

金属学报

2014, Vol. 50

Issue (4): 454-462 DOI: 10.3724/SP.J.1037.2013.00637

本期目录 | 过刊浏览

Ti_0.7Zr_0.3(Cr₁_-_xV_x)₂合金的结构和贮氢性能^*

马坪¹, 吴二冬¹(

), 李武会², 孙凯³, 陈东风³

1 中国科学院金属研究所沈阳材料科学国家(联合)实验室, 沈阳110016
2 河南科技大学材料科学与工程学院, 洛阳 471003
3 中国原子能科学研究院, 北京 102413

MICROSTRUCTURES AND HYDROGEN STORAGE PROPERTIES OF Ti_0.7Zr_0.3(Cr₁_-_xV_x)₂ ALLOYS

MA Ping¹, WU Erdong¹(

), LI Wuhui², SUN Kai³, CHEN Dongfeng³

1 Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016
2 School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471003
3 China Institute of Atomic Energy, Beijing 102413

引用本文:

马坪, 吴二冬, 李武会, 孙凯, 陈东风. Ti_0.7Zr_0.3(Cr₁_-_xV_x)₂合金的结构和贮氢性能^*[J]. 金属学报, 2014, 50(4): 454-462.
Ping MA, Erdong WU, Wuhui LI, Kai SUN, Dongfeng CHEN. MICROSTRUCTURES AND HYDROGEN STORAGE PROPERTIES OF Ti_0.7Zr_0.3(Cr₁_-_xV_x)₂ ALLOYS[J]. Acta Metall Sin, 2014, 50(4): 454-462.

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摘要:

采用XRD和SEM分析了Ti_0.7Zr_0.3(Cr₁_-_xV_x)₂ (x=0.1, 0.2, 0.3, 0.4)合金的相组成、晶体结构和元素成分; 采用Sieverts装置、差热和热重分析仪(DTA-TG)测量了合金的活化性能、吸放氢P-C-T曲线、热力学参数及高温放氢特征. 结果表明, 合金为多相组织, 存在C36(P6₃/mmc)和C15(Fd3m) 2种Laves相和几种晶格常数近似的钒基bcc固溶体相. 当V含量较低时, 合金主要由C36型Laves相和少量bcc固溶体相组成. 随着V含量增加, C36型转变为C15型Laves相, 其中第3种(C层)堆垛存在几率增加, 而且合金中bcc固溶体相含量增加. 合金在2 MPa氢压和常温下能迅速活化; 表面氧化后, x=0.1和0.2合金仍表现出优异的活化性能. 随着V含量增加, 合金的贮氢量增加、平台压力减小. 合金氢化的相对偏摩尔焓变(ΔH)和熵变(ΔS)的变化范围为-7~ -28 kJ/mol和-35~ -95 J/(mol·K). DTA-TG分析表明, 合金氢化物分解主要出现在500~600 K温度区间, 并呈现对应不同类型氢化物的2个分解温度, 加热到800 K时合金中稳定的氢化物完全分解.

关键词 ：贮氢, Laves相, 固溶体相, P-C-T曲线, 热力学, 热重分析

Abstract：

The crystal structures and phase compositions of Ti_0.7Zr_0.3(Cr₁_-_xV_x)₂(x=0.1, 0.2, 0.3, 0.4) alloys are analyzed by the XRD and SEM. The hydrogen storage properties, activation performance, thermodynamics and high-temperature desorption process of the alloys are investigated by pressure-composition-temperature (P-C-T) and DTA-TG measurements. The results show that the Ti_0.7Zr_0.3(Cr₁_-_xV_x)₂ alloys contain multi-phases, i.e. C36 (P6₃/mmc) and C15 (Fd3m) Laves phases and V-based bcc solid solution phases with different lattice constants. When the content of V in the alloy is low, the alloy basically consists of C36 type of Laves phase and small amount of bcc solid solution phase. As the content of V increases, the C36 type transfers into C15 type of Laves phase, where the probability of forming third type of stacking layers (C layers) increases, and the content of the bcc solid solution also increases. The alloys in bulk can be easily activated at 2 MPa and room temperature. The x=0.1, 0.2 alloys present excellent activation performance even after exposure in air for 20 d. As V content increases, the hydrogen absorption capacity of the alloy increases whereas the plateau pressure decreases. The relative partial molar enthalpy (ΔH) and entropy (ΔS) of hydrogen absorption for the alloys are found to be in the ranges of -7~-28 kJ/mol and -35~ -95 J/(mol·K). The DTA-TG analysis indicates that the hydrogen release from the hydrides of the alloys occur in two dissolving temperatures within the range of 500~600 K, and some residual hydrides have completely decomposed at heating temperature up to 800 K.

Key words： hydrogen storage Laves phase solid solution phase pressure-concentration-temperature (P-C-T) curve thermodynamics DTA-TG analysis

收稿日期: 2013-10-10

ZTFLH:

TG139.7

基金资助:*国家自然科学基金项目11079043和国家重点基础研究发展计划项目2010CB833101资助

作者简介: null

马坪, 男, 1983年生, 博士生

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https://www.ams.org.cn/CN/10.3724/SP.J.1037.2013.00637 或 https://www.ams.org.cn/CN/Y2014/V50/I4/454

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