<strong>Y</strong>掺杂<strong>Ti</strong>膜的吸放氢行为

doi:10.11900/0412.1961.2022.00162

金属学报

2024, Vol. 60

Issue (6): 826-836 DOI: 10.11900/0412.1961.2022.00162

研究论文

本期目录 | 过刊浏览

Y掺杂Ti膜的吸放氢行为

李聪, 王猛, 屠汉俊, 施立群(

)

复旦大学现代物理研究所上海 200433

Behavior of Hydrogen Absorption and Desorption in Y-doped Ti Films

LI Cong, WANG Meng, TU Hanjun, SHI Liqun(

)

Institute of Modern Physics, Fudan University, Shanghai 200433, China

引用本文:

李聪, 王猛, 屠汉俊, 施立群. Y掺杂Ti膜的吸放氢行为[J]. 金属学报, 2024, 60(6): 826-836.
Cong LI, Meng WANG, Hanjun TU, Liqun SHI. Behavior of Hydrogen Absorption and Desorption in Y-doped Ti Films[J]. Acta Metall Sin, 2024, 60(6): 826-836.

全文: PDF(2249 KB) HTML

摘要:

合金化方法通常被用于改善储氢金属的力学性能，然而这往往会影响材料的储氢性能。为了研究Y掺杂对金属Ti吸放氢的影响，本工作从实验和模拟2方面研究了Ni/Ti-Y合金薄膜的吸放氢特性。采用直流磁控溅射方法制备不同Y掺杂含量的Ti-Y薄膜，并在表面镀一层Ni膜以减少表面污染。吸氘实验发现，Ti薄膜中氘(D)含量随着Y浓度的增加而增大，这是因为替位Y能够结合更多的D，且Y易与O结合可降低Ti被毒化的程度，有利于Ti吸D。密度泛函理论计算表明Y增强了与其相邻的Ti—H 键能，同时产生了较强的Y—H键，导致紧邻Y的H结合能和扩散势垒增大，Ti-Y对H的束缚力增强；氘热释放实验结果显示Ni/Ti-Y体系的D解吸表观活化能高于纯Ni/Ti，说明Y对Ni/Ti-Y体系的氘脱附动力学产生了重要影响。结果表明Y掺杂对Ti薄膜体系的吸放氢性能都产生了一定程度的影响。

关键词 ：磁控溅射, 离子束分析, 密度泛函理论, 扩散, 表观活化能

Abstract：

Alloying is often used to improve resistance to hydrogen-induced pulverization and cracking of hydrogen storage materials such as titanium and zirconium. However, it often affects the hydrogen storage performance of the material itself. Ti-Y alloys exhibit good mechanical properties, and they can effectively suppress hydrogen embrittlement. The properties of hydrogen absorption and desorption were investigated experimentally and theoretically in the present work. Y was uniformly doped into Ti films as a substitution atom using direct current magnetron sputtering. In addition, a Ni film of about 5 nm was subsequently deposited onto all sample surfaces to reduce surface contamination. Deuterium gas (D₂) was used for hydrogen absorption experiment. Hydrogen absorption results show that the deuterium concentration in Ti-Y films increases with the increase of Y concentration. Combined with the density functional theory (DFT) calculation, the effects of Y doping on the hydrogen absorption properties of Ti could be summarized as follows: (1) the binding energy of Y to H calculated by DFT is stronger than that of Ti, thereby increasing the concentration of D absorbed; (2) Y has a strong affinity for O to form Y₂O₃, which reduces O impurity concentration in Ti film and facilitates more D atoms to enter the Ti lattice to increase the amount of D absorption; (3) Y substitutes for the Ti atom to increase the binding energy of Ti—H adjacent to Y, making the D atom less likely to escape, and to reduce the diffusion barrier of D around Ti, which is distant from Y, making it easy for D to diffuse deeper into the sample. Therefore, the concentration of D absorbed in Ti samples increases with the increase of Y concentration. With regard to the properties of D desorbed in Ti-Y samples, the results show that the D desorption activation energy of the deuteride Ti-Y film could be increased by doping Y. The D desorption temperature is determined by the D thermal desorption kinetics of the Ni/Ti-Y film system, and Y doping may increase the apparent binding energy and diffusion activation energy for D of the overall Ti lattice. The surface potential barrier has an important effect on D desorbed from Ti. Furthermore, Y doping has a certain degree of influence on the hydrogen absorption and desorption performance of Ti thin films.

Key words： magnetron sputtering ion beam analysis density functional theory diffusion apparent activation energy

收稿日期: 2022-04-08

ZTFLH:

O647

通讯作者: 施立群，lqshi@fudan.edu.cn，主要从事离子束应用物理、反应堆材料与物理、功能薄膜物理与技术等研究;

Corresponding author: SHI Liqun, professor, Tel: 13761509463, E-mail: lqshi@fudan.edu.cn

作者简介: 李聪，女，1995年生，博士生
第一联系人：王猛(共同第一作者)，男，1997年生，博士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2022.00162 或 https://www.ams.org.cn/CN/Y2024/V60/I6/826

图1 磁控溅射复合靶示意图

表1 α-Ti与TiH2单胞的结构参数

图2 α-Ti中H扩散路径(黑色箭头)

图3 TiH2中H扩散路径(黑色箭头)

表2 α-Ti和TiH2中氢结合能和扩散激活能计算结果

图4 掺Y前后H原子在α-Ti (Ti32)和TiH2 (Ti32H64)中不同扩散路径需要克服的能量势垒

图5 计算掺Y氢化钛中H的结合能时不同位置H的示意图

表3 掺杂Y前后α-Ti(Ti32)和TiH2(Ti32H64)中原子间键的键级及键长

图6 吸氘前TiY0.13及吸氘后TiY0.13D0.78样品的Rutherford背散射技术(RBS)测量-拟合谱

图7 吸氘后TiY0.13D0.78样品的弹性反冲分析(ERDA)测量-拟合谱

图8 吸氘后不同Y含量的Ti薄膜中的D浓度分布

表4 离子束分析测量吸氘前后的元素含量以及薄膜厚度

图9 吸氘前Ti与TiY0.08薄膜及吸氘后TiD0.63与TiY0.08-D0.73薄膜的GIXRD谱

图10 吸氘后TiD0.63与TiY0.13D0.78的XPS全扫谱，及TiY0.13D0.78中Y3d、TiD0.63与TiY0.13D0.78中Ti2p的XPS窄扫谱

图11 原子氢和分子氢在材料表面和体内的能态图

图12 吸氘后样品的热脱附谱(仅展示D2信号)

图13 TiD0.63和TiY0.13D0.78样品的升温速率与热脱附峰峰温的关系

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