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

doi:10.11900/0412.1961.2022.00162

Acta Metall Sin

2024, Vol. 60

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

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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

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LI Cong, WANG Meng, TU Hanjun, SHI Liqun. Behavior of Hydrogen Absorption and Desorption in Y-doped Ti Films. Acta Metall Sin, 2024, 60(6): 826-836.

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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

Received: 08 April 2022

ZTFLH:

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

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https://www.ams.org.cn/EN/10.11900/0412.1961.2022.00162 OR https://www.ams.org.cn/EN/Y2024/V60/I6/826

Fig.1 Schematic of magnetron sputtering composite target

Structure type	Space group	Space group No.	Cell parameter
			a / nm	b / nm	c / nm	α / (°)	β / (°)	γ / (°)
α-Ti	P6₃/mmc	194	0.29487	0.29487	0.46146	90	90	120
TiH₂	Fm $3 ¯$ m	225	0.44275	0.44275	0.44275	90	90	90

Table 1 Structural parameters of α-Ti and TiH₂ unitcell

Fig.2 H diffusion paths in α-Ti (black arrows) (The blue (including the green), white, and purple balls represent Ti, H, and Y atoms, respectively; O1, O2, O3 represent octahedral interstitial sites (OIS) 1, 2, and 3, respectively; TIS—tetrahedron interstitial sites)

Fig.3 H diffusion paths in TiH₂ (black arrows) (The blue, white, and purple balls represent Ti, H, and Y atoms, respectively; T1, T2 represent TIS 1 and 2, respectively)

Table 2 Calculation results of hydrogen binding energy and diffusion activation energy in α-Ti and TiH₂

Fig.4 Energy barriers for a H atom to need to be overcome in passing through different diffusion paths in α-Ti (Ti₃₂) (a) and TiH₂ (Ti₃₂H₆₄) (b) before and after Y doping

Fig.5 Schematic of H at different positions in calculating the binding energy of H in Y-doped TiH₂ (The gray, orange, green, and pink balls all represent the H atoms of the TiH₂ matrix; the blue and purple balls represent the Ti and Y atoms, respectively; the white ball represents the H atom located in OIS near the Y atom)

Table 3 Bonding order and length of interatomic bonds in α-Ti (Ti₃₂) and TiH₂ (Ti₃₂H₆₄) before and after Y doping

Fig.6 RBS experimental and simulated spectra of TiY_0.13 before (a) and after (b) absorbing deuterium (RBS—Rutherford backscattering spectrometry; insets are the corresponding local enlargements of spectra)

Fig.7 ERDA experimental and simulated spectra of TiY_0.13D_0.78 sample after absorbing deuterium (ERDA—elastic recoil detection analysis)

Fig.8 Depth profiles of D concentration in Ti films with Y concentration after absorbing deuterium (Dashed lines indicate estimated values)

Table 4 Element concentration and film thickness before and after deuterium absorption measured by ion beam analysis

Fig.9 GIXRD spectra of Ti and TiY_0.08 films before (a) and after (b) absorbing deuterium

Fig.10 XPS full scan spectra of TiD_0.63 and TiY_0.13D_0.78 after absorbing deuterium (a), and XPS narrow scan spectra of Y3d in TiY_0.13D_0.78 (b) and Ti2p in TiD_0.63 and TiY_0.13D_0.78 (c)

Fig.11 Energy states of atomic and molecular hydrogen on the surface and in the bulk of metal ( $E s$ is the heat of solution for $12 H 2$ molecules; $E C$ is the energy barrier for conversion of $12 H 2$ molecules to chemisorbed state H; $E C'$ is the energy barrier for conversion of adsorbed H to molecular hydrogen; $E A$ is the energy barrier for transformation of adsorbed H into dissolved H; $E A'$ is the energy barrier for transformation of dissolved H into adsorbed H; $Q D$ is the diffusion activation energy; $E b$ is the binding energy between H and host atom; $E D e$ is the de-trapping activation energy; $E'$ is the saddle point energy)

Fig.12 Thermal desorption spectra of TiD_0.63 (a) and TiY_0.13D_0.78 (b) samples after absorbing deuter-ium (only the D₂ signal is shown)

Fig.13 Relationships between heating rate (v) and thermal desorption peak temperature (T_P) of TiD_0.63 and TiY_0.13D_0.78 (R²—goodness of fit)

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