Study on the hydrogen storage properties of (Ti0.9Zr0.1)1.1Mn1.2-x Cr0.8Ga x alloys

doi:10.19799/j.cnki.2095-4239.2025.0427

Abstract

Abstract:

Gallium (Ga), as a liquid metal with negative mixing enthalpies with multiple elements, can form high-entropy alloys (HEAs) with various metals under mild conditions. In this study, Ga was introduced into C14 Laves phase HEAs. (Ti_0.9Zr_0.1)_1.1Mn_1.2-_x Cr_0.8Ga _x alloys (x = 0, 0.1, 0.2) alloys were fabricated using vacuum induction melting technology. Through a combination of theoretical calculations and experimental tests, the effects of the Ga substitution for Mn on the microstructure and hydrogen storage properties were systematically investigated. Theoretical calculations revealed that Ga doping reduced the atomic size difference from 7.54 to 7.39 and lowered the mixing enthalpy to -9.17 kJ/mol, thereby improving the phase stability. The valence electron concentration analysis suggested an efficient hydrogen absorption/desorption performance at ambient temperature. The experimental results demonstrated that all alloys exhibited single-phase C14 Laves structures with a homogeneous elemental distribution. Ga substitution for Mn increased the unit cell volume from 165.52 Å³ to 167.25 Å³, significantly reducing the hydrogen absorption/desorption plateau pressures and hysteresis factors while improving the kinetic performance. The time required to reach 90% of the maximum hydrogen capacity was shortened to less than 50 s. Among the tested alloys, (Ti_0.9Zr_0.1)_1.1Mn_1.1Cr_0.8Ga_0.1 displayed the optimal hydrogen storage properties, achieving a maximum capacity of 1.81% (weight fraction) with absorption/desorption plateau pressures of 0.9 MPa and 0.86 MPa at 293 K, respectively. This alloy retained 96% of its initial capacity after 30 cycles while maintaining a single C14 Laves phase, demonstrating exceptional cycling stability. This study clarifies the mechanistic role of Ga in high-entropy hydrogen storage alloys and provides theoretical guidance for Ga applications in hydrogen storage materials.

Key words: gallium, hydrogen storage alloy, hydrogen storage properties, C14 Laves phase

CLC Number:

TK 91

Bin YANG, Mianheng ZHANG, Changying ZHAO, Xia LONG. Study on the hydrogen storage properties of (Ti_0.9Zr_0.1)_1.1Mn_1.2_-_x Cr_0.8Ga _x alloys[J]. Energy Storage Science and Technology, 2025, 14(10): 3666-3676.

Figures/Tables 15

Table 1

Parameters of the (Ti0.8Zr0.2)1.1Mn1.2Cr0.8-x Ga x alloys"

原子尺寸差

混合熵 $∆ S m i x$

/[J/(K·mol)]

混合焓 $∆ H m i x$

/(kJ/mol)

Ω

价电子浓度

VEC

7.54

9.98

-6.51

2.13

5.55

0.1

7.47

10.9

-7.84

1.72

5.45

0.2

7.39

11.43

-9.17

1.43

5.35

Table 1

Table 2

Fig. 1

Table 3

Fig. 2

Fig. 3

Table 4

Hydrogen absorption and desorption parameters of (Ti0.9Zr0.1)1.1Mn1.2-x Cr0.8Ga x"

样品	T/K	$P a$ /MPa	$P d$ /MPa	H_f	S_f	C_max/%	C_use/%
x=0	293	1.45	1.11	0.269	2.38	1.83	1.63
	313	2.26	1.81	0.220	2.27	1.77	1.60
	333	3.14	2.67	0.163	1.61	1.23	1.09

x=0.1	293	0.90	0.86	0.045	2.47	1.81	1.47
	313	1.48	1.39	0.063	2.53	1.62	1.41
	333	2.25	2.11	0.064	3.39	1.56	1.32

x=0.2	293	0.67	0.63	0.062	2.18	1.41	1.17
	313	0.98	0.89	0.096	3.19	1.25	0.99
	333	1.29	1.27	0.016	2.75	1.21	1.03

Table 4

Fig. 4

Table 5

Thermodynamic parameters of the (Ti0.9Zr0.1)1.1Mn1.2-x Cr0.8Ga x (x=0, 0.1, 0.2) alloys"

样品	$∆ H a$ /(kJ/mol)	$∆ H d$ /(kJ/mol)	$∆ S a$ /[J/(mol·K)]	$∆ S d$ /[J/(mol·K)]
x=0	-15.64	17.79	-75.72	80.80
x=0.1	-18.45	18.26	-81.31	80.21
x=0.2	-13.15	14.68	-60.73	65.27

Table 5

Fig. 5

Fig. 6

Fig. 7

Table 6

Fig. 8

Fig. 9

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样品		成分/%
样品		Ti	Zr	Mn	Cr	Ga
x=0	设计	28.78	6.06	39.97	25.19	0
x=0	ICP	28.97	5.86	39.14	26.03	0

x=0.1	设计	28.52	6.07	36.30	24.97	4.20
x=0.1	ICP	28.04	5.80	36.34	25.19	4.63

x=0.2	设计	28.26	5.95	32.71	24.74	8.33
x=0.2	ICP	27.67	5.76	32.15	25.55	8.87

样品	a/Å	c/Å	a/c	V/Å³
(Ti_0.9Zr_0.1)_1.1Mn_1.2Cr_0.8	4.88520	8.00854	0.6100	165.52
(Ti_0.9Zr_0.1)_1.1Mn_1.1Cr_0.8Ga_0.1	4.88927	8.01494	0.6100	165.93
(Ti_0.9Zr_0.1)_1.1Mn_1.0Cr_0.8Ga_0.2	4.90495	8.02739	0.6110	167.25

样品	a/Å	c/Å	a/c	V/Å³
循环前	4.88927	8.01494	0.6100	165.93
30次循环后	4.89559	8.02403	0.6101	166.55