Solid-State Hydrogen Storage Properties of Ti-V-Nb-Cr High-Entropy Alloys and the Associated Effects of Transitional Metals (M = Mn, Fe, Ni)

doi:10.1007/s40195-022-01403-9

Abstract

Abstract:

Recently, high-entropy alloys (HEAs) designed by the concepts of unique entropy-stabilized mechanisms, started to attract widespread interests for their hydrogen storage properties. HEAs with body-centered cubic (BCC) structures present a high potential for hydrogen storage due to the high hydrogen-to-metal ratio (up to H/M = 2) and vastness of compositions. Although many studies reported rapid absorption kinetics, the investigation of hydrogen desorption is missing, especially in BCC HEAs. We have investigated the crystal structure, microstructure and hydrogen storage performance of a series of HEAs in the Ti-V-Nb-Cr system. Three types of TiVCrNb HEAs (Ti₄V₃NbCr₂, Ti₃V₃Nb₂Cr₂, Ti₂V₃Nb₃Cr₂) with close atomic radii and different valence electron concentrations (VECs) were designed with single BCC phase by CALPHAD method. The three alloys with fast hydrogen absorption kinetics reach the H/M ratio up to 2. Particularly, Ti₄V₃NbCr₂ alloy shows the hydrogen storage capacity of 3.7 wt%, higher than other HEAs ever reported. The dehydrogenation activation energy of HEAs’ hydride has been proved to decrease with decreasing VEC, which may be due to the weakening of alloy atom and H atom. Moreover, Ti₄V₃NbCr₂M (M = Mn, Fe, Ni) alloys were also synthesized to destabilize hydrides. The addition of Mn, Fe and Ni lead to precipitation of Laves phase, however, the kinetics did not improve further because of their own excellent hydrogen absorption. With increasing the content of Laves phase, there appear more pathways for hydrogen desorption so that the hydrides are more easily dissociated, which may provide new insights into how to achieve hydrogen desorption in BCC HEAs at room temperature.

Key words: High-entropy alloy, Hydrogen storage, CALPHAD, Hydride stability, Hydrogen sorption kinetics

Bo Cheng, Yunkai Li, Xiaoxi Li, Huibin Ke, Liang Wang, Tangqing Cao, Di Wan, Benpeng Wang, Yunfei Xue. Solid-State Hydrogen Storage Properties of Ti-V-Nb-Cr High-Entropy Alloys and the Associated Effects of Transitional Metals (M = Mn, Fe, Ni)[J]. Acta Metallurgica Sinica (English Letters), 2023, 36(7): 1113-1122.

Figures/Tables 10

Fig. 1 Calculated phase diagram through Thermo-calc software and TCHEA3 database of a Ti4V3NbCr2 alloy, b Ti3V3Nb2Cr2 alloys, c Ti2V3Nb3Cr2 alloy

Fig. 2 BSE-SEM micrographs for a Ti4V3NbCr2, b Ti3V3Nb2Cr2, c Ti2V3Nb3Cr2

Fig. 3 XRD patterns of Ti4V3NbCr2, Ti3V3Nb2Cr2 and Ti2V3Nb3Cr2 at initial as-cast state a and after hydrogen absorption b, respectively. Insets in a showing the element mapping using EDS of the arc-melted ingots

Table 1 Crystallographic data of Ti-V-Nb-Cr series alloys as designed

Alloys	VEC	Phase structure	Designed atom radius (Å)	Lattice parameters (Å)	Unit cell volume (Å³)
Ti₄V₃NbCr₂	4.8	BCC	1.39	3.139	30.93
Ti₃V₃Nb₂Cr₂	4.9	BCC	1.39	3.135	30.81
Ti₂V₃Nb₃Cr₂	5	BCC	1.39	3.142	31.01

Fig. 4 a Hydrogen sorption kinetics of samples in the first cycle under 50 bar H2 at 300 K, b PCT curves of the alloy samples after 1st cycle hydrogen absorption/desorption at 323 K

Table 2 Hydrogen storage properties of alloys

Alloys	Structure	Maximum capacity (wt%)	H/M
Ti₄V₃NbCr₂	BCC	3.7	2.01
Ti₃V₃Nb₂Cr₂	BCC	3.4	1.99
Ti₂V₃Nb₃Cr₂	BCC	3.2	2.02
V₅₅Ti_20.5Cr_18.1Fe_6.4 [52]	BCC	3.5	1.78
TiV_1.1Mn_0.9 [51]	BCC	2.99	1.53

Fig. 5 DSC curves of hydrogenated alloys: a Ti4V3NbCr2, b Ti3V3Nb2Cr2, c Ti2V3Nb3Cr2

Fig. 6 XRD of Ti4V3NbCr2M (M = Mn, Fe, Ni) as-cast alloys a and its hydrides b, SEM micrographs for c Ti4V3NbCr2Mn, d Ti4V3NbCr2Fe, e Ti4V3NbCr2Ni

Table 3 Elemental distribution (at.%) of the Ti4V3NbCr2M (M = Mn, Fe, Ni) alloys

Alloys	Phase	Ti	V	Nb	Cr	Mn	Fe	Ni
Ti₄V₃NbCr₂Mn	BCC	36.25	25.32	10.54	17.55	10.34	-	-
Ti₄V₃NbCr₂Mn	Secondary phase	39.16	21.43	9.54	15.43	14.44	-	-
Ti₄V₃NbCr₂Fe	BCC	35.57	26.01	11.11	18.35	-	8.97	-
Ti₄V₃NbCr₂Fe	Secondary phase	37.83	14.48	7.2	13.69	-	26.81	-
Ti₄V₃NbCr₂Ni	BCC	33.05	29.14	12.75	19.77	-	-	5.30
Ti₄V₃NbCr₂Ni	Secondary phase	48.40	5.82	4.34	5.81	-	-	35.64

Fig. 7 a Hydrogen sorption kinetics of Ti4V3NbCr2M (M = Mn, Fe, Ni) alloys, b PCT curves of the alloy samples after 1st cycle hydrogen absorption/desorption at 323 K, c DSC curves of hydrogenated alloys at 10 K/min heating rate

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