Enhancement of hydrogenation kinetics and thermodynamic properties of ZrCo1−xCrx (x = 0−0.1) alloys for hydrogen storage

Linling Luo; Xiaoqiu Ye; Guanghui Zhang; Huaqin Kou; Renjin Xiong; Ge Sang; Ronghai Yu; Dongliang Zhao

doi:10.1088/1674-1056/ab9289

Chinese Physics B, Volume. 29, Issue 8, (2020)

Enhancement of hydrogenation kinetics and thermodynamic properties of ZrCo_1−xCr_x (x = 0−0.1) alloys for hydrogen storage

Linling Luo¹, Xiaoqiu Ye¹, Guanghui Zhang², Huaqin Kou², Renjin Xiong², Ge Sang^2、†, Ronghai Yu³, and Dongliang Zhao⁴

Author Affiliations

¹Science and Technology on Surface Physics and Chemistry Laboratory, Mianyang 62907, China

²Institute of Materials, China Academy of Engineering Physics, Mianyang 61900, China

³School of Materials Science and Engineering, Beihang University, Beijing 100191, China

⁴Department of Functional Material Research, Central Iron and Steel Research Institute, Beijing 100081, China

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Figures & Tables(19)

Fig. 1. XRD spectra of ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.

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Fig. 2. XRD spectra of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems.

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Fig. 3. EDS mappings of ZrCo_0.95Cro_0.05 alloy.

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Fig. 4. First hydrogenation kinetics of ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys under 4-bar H₂ at 348 K.

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Fig. 5. Initial hydriding kinetic curves for ZrCo (a) and ZrCo_0.95Cr_0.05 (b) alloys at 323 K, 348 K, and 373 K.

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Fig. 6. Plots of ln(−ln(1 − α)) versus ln t for the hydrogenation of ZrCo (a) and ZrCo_0.95Cr_0.05 (b) alloys.

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Fig. 7. Plots of ln kversus 1000/T for the hydrogenation of ZrCo and ZrCo_0.95Cr_0.05 alloys.

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Fig. 8. PCT curves of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems.

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Fig. 9. Van’t Hoff curves for ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems.

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Fig. 10. Hydrogen pressure evolution of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems at 798 K insulated for 10 h.

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Fig. 11. XRD patterns of disproportionation products of ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.

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Fig. 12. The isothermal disproportionation curves of ZrCo (a) and ZrCo_0.95Cr_0.05 (b) samples.

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Fig. 13. Plots of ln(−ln(1 − α)) versus ln t for the disproportionation of ZrCo (a) and ZrCo_0.95Cr_0.05 (b) alloys at different temperatures.

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Fig. 14. Plots of ln kversus 1000/T for the disproportionation of ZrCo and ZrCo_0.95Cr_0.05 alloys.

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Table 1. Lattice parameters and cell volume of ZrCo phase in ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.
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Table 1. Lattice parameters and cell volume of ZrCo phase in ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.
Samples Lattice parameters/Å Cell volume/Å³
x = 0 3.1912 32.4984
x = 0.025 3.1917 32.5137
x = 0.05 3.1921 32.5259
x = 0.075 3.1936 32.5718
x = 0.1 3.1944 32.5963

Table 2. Average chemical composition (atom%) for ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.
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Table 2. Average chemical composition (atom%) for ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.
Samples Zr L Co K Cr K
x = 0 48.36 51.64
x = 0.025 48.08 50.14 1.78
x = 0.05 47.50 49.34 3.16
x = 0.075 47.40 48.12 4.48
x = 0.1 48.24 46.26 5.50

Table 3. Initial activation behaviors of ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys under 4-bar H₂ at 348 K. Incubation period: the time needed to begin hydrogen absorption. Activation time: the time needed to reach 95% of saturated hydrogen capacity.
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Table 3. Initial activation behaviors of ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys under 4-bar H₂ at 348 K. Incubation period: the time needed to begin hydrogen absorption. Activation time: the time needed to reach 95% of saturated hydrogen capacity.
Samples Incubation period/s Activation time/s Hydrogen absorption capability/(H(f.u.))
x = 0 30 7715 2.896
x = 0.025 14 3138 2.822
x = 0.05 9 1316 2.803
x = 0.075 7 759 2.774
x = 0.1 6 195 2.679

Table 4. Thermodynamic characteristics for hydrogen desorption of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems.

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Table 4. Thermodynamic characteristics for hydrogen desorption of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems.

Systems	ΔH/(kJ/mol H₂)	ΔS/(kJ/mol⋅K H₂)
ZrCo–H^[19]	89.71	226.16
ZrCo–H	90.41	233.45
ZrCo_0.975Cr_0.025−H	91.02	234.34
ZrCo_0.95Cr_0.05−H	91.80	235.59
ZrCo_0.925Cr_0.725−H	92.33	236.38
ZrCo_0.9Cr_0.1−H	92.54	236.48

Table 5. Disproportionation behaviors of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems at 798 K insulated for 10 h. Absorbed pressure is the change in hydrogen pressure of activation process at room temperature.

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Table 5. Disproportionation behaviors of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems at 798 K insulated for 10 h. Absorbed pressure is the change in hydrogen pressure of activation process at room temperature.

Sample	Absorbed pressure/kPa	Initial pressure/kPa	Ending pressure/kPa	Remaining pressure/kPa	Extent of degradation/%
x = 0	130.14	130.7	91.8	72.6	83.68
x = 0.025	126.73	125.1	86.6	68.2	80.72
x = 0.05	126.04	124	86.4	64.9	77.24
x = 0.075	119.7	114	80.5	59.9	75.06
x = 0.1	112.73	106	75.4	53	70.52

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Linling Luo, Xiaoqiu Ye, Guanghui Zhang, Huaqin Kou, Renjin Xiong, Ge Sang, Ronghai Yu, Dongliang Zhao. Enhancement of hydrogenation kinetics and thermodynamic properties of ZrCo_1−xCr_x (x = 0−0.1) alloys for hydrogen storage[J]. Chinese Physics B, 2020, 29(8):

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Paper Information

Received: Feb. 8, 2020

Accepted: --

Published Online: Apr. 29, 2021

The Author Email: Sang Ge (anglesg@163.com)

DOI:10.1088/1674-1056/ab9289

Topics

Nuclear physics

Particles and fields

Particle and nuclear astrophysics and cosmology

Table 1. Lattice parameters and cell volume of ZrCo phase in ZrCo1 − xCrx (x = 0−0.1) alloys.

Table 1. Lattice parameters and cell volume of ZrCo phase in ZrCo1 − xCrx (x = 0−0.1) alloys.

Table 2. Average chemical composition (atom%) for ZrCo1 − xCrx (x = 0−0.1) alloys.

Table 2. Average chemical composition (atom%) for ZrCo1 − xCrx (x = 0−0.1) alloys.

Table 3. Initial activation behaviors of ZrCo1 − xCrx (x = 0−0.1) alloys under 4-bar H2 at 348 K. Incubation period: the time needed to begin hydrogen absorption. Activation time: the time needed to reach 95% of saturated hydrogen capacity.

Table 3. Initial activation behaviors of ZrCo1 − xCrx (x = 0−0.1) alloys under 4-bar H2 at 348 K. Incubation period: the time needed to begin hydrogen absorption. Activation time: the time needed to reach 95% of saturated hydrogen capacity.

Table 4. Thermodynamic characteristics for hydrogen desorption of ZrCo1 − xCrx (x = 0−0.1)−H systems.

Table 4. Thermodynamic characteristics for hydrogen desorption of ZrCo1 − xCrx (x = 0−0.1)−H systems.

Table 5. Disproportionation behaviors of ZrCo1 − xCrx (x = 0−0.1)−H systems at 798 K insulated for 10 h. Absorbed pressure is the change in hydrogen pressure of activation process at room temperature.

Table 5. Disproportionation behaviors of ZrCo1 − xCrx (x = 0−0.1)−H systems at 798 K insulated for 10 h. Absorbed pressure is the change in hydrogen pressure of activation process at room temperature.

Table 1. Lattice parameters and cell volume of ZrCo phase in ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.

Table 1. Lattice parameters and cell volume of ZrCo phase in ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.

Table 2. Average chemical composition (atom%) for ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.

Table 2. Average chemical composition (atom%) for ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys.

Table 3. Initial activation behaviors of ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys under 4-bar H₂ at 348 K. Incubation period: the time needed to begin hydrogen absorption. Activation time: the time needed to reach 95% of saturated hydrogen capacity.

Table 3. Initial activation behaviors of ZrCo_{1 − x}Cr_x (x = 0−0.1) alloys under 4-bar H₂ at 348 K. Incubation period: the time needed to begin hydrogen absorption. Activation time: the time needed to reach 95% of saturated hydrogen capacity.

Table 4. Thermodynamic characteristics for hydrogen desorption of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems.

Table 4. Thermodynamic characteristics for hydrogen desorption of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems.

Table 5. Disproportionation behaviors of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems at 798 K insulated for 10 h. Absorbed pressure is the change in hydrogen pressure of activation process at room temperature.

Table 5. Disproportionation behaviors of ZrCo_{1 − x}Cr_x (x = 0−0.1)−H systems at 798 K insulated for 10 h. Absorbed pressure is the change in hydrogen pressure of activation process at room temperature.