Ti0.7Zr0.3(Cr1-xVx)2合金的结构和贮氢性能*
马 坪, 男, 1983年生, 博士生
收稿日期: 2013-10-10
修回日期: 2013-12-16
网络出版日期: 2014-04-20
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
MICROSTRUCTURES AND HYDROGEN STORAGE PROPERTIES OF Ti0.7Zr0.3(Cr1-xVx)2 ALLOYS
Received date: 2013-10-10
Revised date: 2013-12-16
Online published: 2014-04-20
Supported by
Supproted by Natioal Natural Science Foundation of China (No.11079043) and National Basic Research Program of China (No.2010CB833101)
采用XRD和SEM分析了Ti0.7Zr0.3(Cr1-xVx)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.
马坪 , 吴二冬 , 李武会 , 孙凯 , 陈东风 . Ti0.7Zr0.3(Cr1-xVx)2合金的结构和贮氢性能*[J]. 金属学报, 2014 , 50(4) : 454 -462 . DOI: 10.3724/SP.J.1037.2013.00637
The crystal structures and phase compositions of Ti0.7Zr0.3(Cr1-xVx)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 Ti0.7Zr0.3(Cr1-xVx)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.
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