Y掺杂Ti膜的吸放氢行为
收稿日期: 2022-04-08
修回日期: 2022-05-22
网络出版日期: 2022-09-05
Behavior of Hydrogen Absorption and Desorption in Y-doped Ti Films
Received date: 2022-04-08
Revised date: 2022-05-22
Online published: 2022-09-05
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。
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 . DOI: 10.11900/0412.1961.2022.00162
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.
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