Compositional dependence of hydrogenation performance of Ti-Zr-Hf-Mo-Nb high-entropy alloys for hydrogen/tritium storage

doi:10.1016/j.jmst.2019.08.060

Abstract

Abstract:

A series of Ti-Zr-Hf-Mo-Nb high-entropy alloys with different Mo concentrations were developed as candidate materials for hydrogen/tritium storage in solid phase. The crystal structures and hydrogenation properties of the Ti-Zr-Hf-Mo-Nb alloys were investigated by X-ray diffraction and differential scanning calorimetry techniques. All the alloys have a body-centred cubic single phase structure. The results demonstrate that the cell volume of the Ti-Zr-Hf-Mo-Nb hydride decreases with increasing Mo concentration, which reduces their thermal stability. The theoretical calculation proposes that the lower binding energy of the Ti-Zr-Hf-Mo-Nb hydride decreases the thermal stability of Ti-Zr-Hf-Mo-Nb alloys with higher Mo content. The great hydrogenation performance for all the Ti-Zr-Hf-Mo-Nb alloys is owing to their reversible single-phase transformation during the hydrogen absorption-desorption cycle, which would be beneficial to improving the hydrogen recycling rate and preventing the disproportionation. The compositional dependence of the hydrogenation performance of the Ti-Zr-Hf-Mo-Nb alloys was established and will be useful in designing novel hydrogen/tritium storage materials to satisfy the requirements of different application fields in hydrogen, solar thermal and nuclear energy.

Key words: High-entropy alloy, Hydrogen/tritium storage, Crystal structure, Phase transformation, Binding energy

Huahai Shen, Jutao Hu, Pengcheng Li, Gang Huang, Jianwei Zhang, Jinchao Zhang, Yiwu Mao, Haiyan Xiao, Xiaosong Zhou, Xiaotao Zu, Xinggui Long, Shuming Peng. Compositional dependence of hydrogenation performance of Ti-Zr-Hf-Mo-Nb high-entropy alloys for hydrogen/tritium storage[J]. J. Mater. Sci. Technol., 2020, 55: 116-125.

Figures/Tables 13

Table 1 Sample designation, atomic-size difference (δ), mixing entropy (△Smix), and mixing enthalpy (△Hmix) of the Ti-Zr-Hf-Mo-Nb alloys with different Mo concentrations. The compositions of the HEA alloys determined by EDS technique were in accord with the designed compositions.

Sample designation	Designed composition (atomic ratio)	EDS composition (atomic ratio)	δ (%)	△S_mix (J K^-1 mol^-1)	△H_mix (kJ mol^-1)
HEA-Mo0	Ti_0.20Zr_0.20Hf_0.20Nb_0.40	Ti_0.21Zr_0.19Hf_0.20Nb_0.40	5.51	11.1	1.28
HEA-Mo10	Ti_0.20Zr_0.20Hf_0.20Mo_0.10Nb_0.30	Ti_0.21Zr_0.20Hf_0.20Mo_0.09Nb_0.31	6.13	12.9	0.56
HEA-Mo20	Ti_0.20Zr_0.20Hf_0.20Mo_0.20Nb_0.20	Ti_0.20Zr_0.18Hf_0.21Mo_0.20Nb_0.21	6.67	13.4	-1.6
HEA-Mo30	Ti_0.20Zr_0.20Hf_0.20Mo_0.30Nb_0.10	Ti_0.21Zr_0.22Hf_0.21Mo_0.27Nb_0.09	7.14	12.9	-3.28
HEA-Mo40	Ti_0.20Zr_0.20Hf_0.20Mo_0.40	Ti_0.21Zr_0.20Hf_0.20Mo_0.39	7.57	11.1	-4.48

Fig. 1. XRD patterns of the synthesized Ti-Zr-Hf-Mo-Nb HEA alloys. All the alloys show a single phase with a BCC crystal structure. The diffraction peaks shift towards higher angles with increasing Mo concentration.

Table 2 Average atomic radius, crystal structure, and lattice constants of the synthesized Ti-Zr-Hf-Mo-Nb HEA alloys. The grain sizes of these alloys were analysed by EBSD from the mechanically polished samples.

Sample designation	Average atomic radius (nm)	Crystal structure	Lattice constant (nm)	Grain size (μm)
HEA-Mo0	0.151	BCC	0.3423(1)	235.5 ± 129.6
HEA-Mo10	0.150	BCC	0.3402(2)	/
HEA-Mo20	0.150	BCC	0.3370(1)	162.8 ± 123.5
HEA-Mo30	0.149	BCC	0.3357(1)	169.1 ± 92.6
HEA-Mo40	0.148	BCC	0.3327(1)	218.8 ± 205.8

Fig. 2. (a) SEM image of HEA-Mo20 alloy. The EDS maps of (b) Ti, (c) Zr, (d) Hf, (e) Mo and (f) Nb elements on the sample surface of (a), showing homogeneous distributions of all five metal elements.

Fig. 3. XRD patterns of before hydrogenation, after hydrogenation and after dehydrogenation for the (a) HEA-Mo0, (b) HEA-Mo10, (c) HEA-Mo20, (d) HEA-Mo30 and (e) HEA-Mo40 alloys. All the alloys present reversible single-phase transformation during the hydrogenation cycles.

Fig. 4. TG (a) and DSC (b) curves of Ti-Zr-Hf-Mo-Nb HEA alloys during heating to 1000 °C.

Table 3 Crystal structure, lattice constants, and cell volumes of the synthesized Ti-Zr-Hf-Mo-Nb HEA alloys. The hydrogen dissociation temperatures and the hydrogen storage capacities were obtained from the DSC and TG curves, respectively.

Sample designation	Crystal structure	Lattice constant (nm)	Cell volume (nm³)	Desorption remperature from DSC curves (°C)	Hydrogen capacity from TG curves (wt%)
HEA-Mo0	FCC	0.4644(2)	0.1002	383	1.12
HEA-Mo10	FCC	0.4608(3)	0.0978	332	1.54
HEA-Mo20	FCC	0.4590(1)	0.0967	302	1.18
HEA-Mo30	BCT	a = 0.3236(1) c = 0.4522(2)	0.0948	164	1.40
HEA-Mo40	BCT	a = 0.3256(2) c = 0.4551(2)	0.0965	168	0.92

Fig. 5. Dependence of cell volume and hydrogen desorption temperature of Ti-Zr-Hf-Mo-Nb hydrides on the Mo concentration. The cell volume of the Ti-Zr-Hf-Mo-Nb HEA alloys decreases with increasing Mo concentration to 27 at.%, which induces the sharply decreased hydrogen desorption temperature from 383 °C to 164 °C.

Fig. 6. Geometrical structures of (a) the Ti-Zr-Hf-Mo-Nb alloys and (b) their hydrides (Mo content = 0, 0.2 and 0.4). The purple, green, yellow, red and pink spheres represent Ti, Zr, Hf, Mo and Nb atoms, respectively. The hydrogen atoms are represented by the wine-colored smaller spheres.

Fig. 7. Volume variation of Ti-Zr-Hf-Mo-Nb alloys with Mo content (Mo content = 0, 0.2 and 0.4) before and after hydrogenation.

Table 4 Average metal-hydrogen distances (d<M-H>) in the hydrides of HEA-Mo0, HEA-Mo20 and HEA-Mo40. The dave.<M-H> is the average distances for all the < metal-hydrogen > bonds.

HEA Hydrides	Distance (nm)
HEA Hydrides	d_<Ti-H>	d_<Zr-H>	d_<Hf-H>	d_<Mo-H>	d_<Nb-H>	d_ave.<_M_-H>
HEA-Mo0	0.1965	0.2099	0.2052	-	0.1983	0.2014
HEA-Mo20	0.1966	0.2084	0.2049	0.1902	0.1958	0.1992
HEA-Mo40	0.1954	0.2079	0.2052	0.1897	-	0.1976

Fig. 8. Binding energy and formation enthalpy of Ti-Zr-Hf-Mo-Nb hydrides (Mo content = 0, 0.2 and 0.4).

Table 5 Average distances for <M-M> bond (d<M-M>, M=Ti, Zr, Hf, Mo, Nb) in HEA-Mo0, HEA-Mo20 and HEA-Mo40 hydrides.

HEA hydrides	Distance (nm)
HEA hydrides	d_<Ti-_M_>	d_<Zr-_M_>	d_<Hf-_M_>	d_<Mo-_M_>	d_<Nb-_M_>
HEA-Mo0	0.3308	0.3333	0.3327	-	0.3328
HEA-Mo20	0.3275	0.3343	0.3326	0.3227	0.3319
HEA-Mo40	0.3222	0.3289	0.3273	0.3278	-

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