Effects of Mo substitution on the kinetic and thermodynamic characteristics of ZrCo1-xMox (x = 0–0.2) alloys for hydrogen storage

Luo, Linling; Ye, Xiaoqiu; Zhao, Cong; Zhang, Guanghui; Kou, Huaqin; Xiong, Renjin; Ge, Shenguang; Han, Tao

doi:10.1016/j.ijhydene.2019.11.126

Cited by 17 publications

(15 citation statements)

References 35 publications

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“…Moreover, the ZrCo phase diagram and EDX analysis were used to ensure the accuracy of the results. The ZrCo reaction can easily form ZrCo 2 , Zr 6 Co 23 , and Zr 2 Co 11 phases below approximately 1800 K when the Co content is higher than 65 at%, 40,41 consistent with previous reports 15,19,24 . As shown in Figure 3E, the composition of the ZrV 0.24 Co 1.76 phase was confirmed by combining XRD and EDX spectroscopy.…”

Section: Resultssupporting

confidence: 89%

“…As shown in Figure 4A, the hydrogenation kinetics of the Zr 50‐ x V x Co 50 ( x = 2.5, 3.5, 5) alloys are considerably enhanced, but the hydrogen absorption capacity decreases after the initial activation, as the increased amount of the nonhydrogen‐absorbing second phase occupies the grain boundary, thus shrinking the effective storage sites for hydrogen in the tetrahedron and octahedron 18,42 . Similarly, a considerable decrease in the hydrogenation capacity of the ZrCo 1‐ x Mo x ( x = 0‐0.2) alloys was observed because the ZrMo 2 second phase did not form hydrides under hydrogen pressure 15 . The addition of Mn to replace Co in the ZrCo alloy exhibited the same behavior 18 …”

Section: Resultsmentioning

confidence: 99%

“…Elemental doping to optimize the properties of ZrCo has led to outstanding achievements. In terms of kinetic properties, Co replaced by Mn, Nb, Mo, and Fe largely reduces the activation time and increases the activation rate 15,18,19 . The temperature and pressure affect the hydriding/dehydriding kinetics of the ZrCo alloy 20‐22 .…”

Section: Introductionmentioning

confidence: 99%

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Effects of V doping on microstructure, kinetic, and thermodynamic characteristics of Zr _{50‐
x} V _x Co ₅₀ ( x = 0, 2.5, 3.5, and 5.0) hydrogen storage alloys

Liang

Wang

et al. 2022

Intl J of Energy Research

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Summary To improve the kinetic properties of the ZrCo alloy, Zr50‐xVxCo50 (x = 0, 2.5, 3.5, and 5.0) samples were fabricated by vacuum arc‐melting. The effects of the V substitution on the microstructure, hydrogen absorption/desorption kinetics, cycling stability, and antidisproportionation properties of ZrCo were systematically investigated. X‐ray diffraction results show that the Zr50‐xVxCo50 (x = 2.5, 3.5, and 5.0) alloys consisted of ZrCo phase and ZrV0.24Co1.76 second phase. The lattice parameter and cell volume gradually decreased with the increase in the V content. The initial activation behavior was improved for the Zr50‐xVxCo50 (x = 2.5, 3.5, and 5.0) samples because of the catalytic effect of the ZrV0.24Co1.76 second phase. Additionally, the equilibrium pressure of hydrogen absorption increased and the plateau width decreased with the increase in the V content. To obtain thermodynamic and kinetic data, ΔH and Ea were calculated using the Van't Hoff equation and Kissinger equation. ΔH of the Zr50‐xVxCo50 (x = 0, 2.5, 3.5, and 5.0)‐H system was reduced from 90.12 to 72.52 kJ·mol−1, while Ea of ZrCoH3 decreased from 113.38 ± 4.2 to 94.13 ± 2.9 kJ·mol−1 for hydrogen desorption, which is beneficial for the hydrogenation/dehydrogenation reaction. Furthermore, the cycling stability and antidisproportionation properties were enhanced after the V addition, particularly for the Zr47.5V2.5Co50 alloy exhibiting an excellent initial activation behavior.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

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Effects of V doping on microstructure, kinetic, and thermodynamic characteristics of Zr _{50‐
x} V _x Co ₅₀ ( x = 0, 2.5, 3.5, and 5.0) hydrogen storage alloys

Liang

Wang

et al. 2022

Intl J of Energy Research

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“…Therefore, in order to restrain the occurrence of disproportionation and explore its mechanism, researchers tried the method of element substitution, with the precondition that the hydrogen absorption and desorption ability of the alloy cannot be destroyed. In fact, researchers have tried many substitute elements (Cu, Cr, Mn, Al, Fe, Ni, Ti, Hf, Sc) [ 61 , 62 , 63 , 64 , 65 , 66 , 67 ]. For example, Hf and Zr are in the same main family, and HfCo and ZrCo have the same structure of CsCl.…”

Section: Effects Of Element Substitution On Anti-disproportionatiomentioning

confidence: 99%

Research Progress on the Anti-Disproportionation of the ZrCo Alloy by Element Substitution

Wang

et al. 2020

Materials

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Hydrogen-induced disproportionation (HID) during the cycles of absorption and desorption leads to a serious decline in the storage capacity of the ZrCo alloy, which has been recognized as the biggest obstacle to its application. Therefore, the prerequisite of a ZrCo application is to solve its anti-disproportionation problem in the field of rapid hydrogen isotope storage. Beyond surface modification and nanoball milling, this work systematically reviews the method of element substitution, which can obviously improve the anti-disproportionation. From a micro angle, as hydrogen atoms that occupy the 8e site in the ZrCoH3 lattice are instable and are considered to be the driving force of disproportionation, researchers believe that element substitution by changing the occupation of hydrogen atoms at the 8e site can improve the anti-disproportionation of the alloy. At present, Ti/Nb substitutions for the Zr terminal among substitute elements have an excellent anti-disproportionation performance. In this work, up-to-date research studies on anti-disproportionation and its disproportionation mechanism of the ZrCo alloy are introduced by combining experiments and simulations. Moreover, the optimization of the alloy based on the occupation mechanism of 8e sites is expected to improve the anti-disproportionation of the ZrCo alloy.

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“…However, uranium has many defects as well, such as spontaneous combustion after the storage of T, being radioactive, and being easy to pulverize. Intermetallic alloy ZrCo is a good substitute [5][6][7][8][9][10][11]. ZrCo has a lower equilibrium pressure of T absorption and a high T absorption [12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Influence of Alloy Atoms on Substitution Properties of Hydrogen by Helium in ZrCoH3

et al. 2021

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Intermetallic alloy ZrCo is a good material for storing tritium (T). However, ZrCo is prone to disproportionation reactions during the process of charging and discharging T. Alloying atoms are often added in ZrCo, occupying the Zr or Co site, in order to restrain disproportionation reactions. Meanwhile, T often decays into helium (He), and the purity of T seriously decreases once He escapes from ZrCo. Therefore, it is necessary to understand the influence of alloying atoms on the basic stability property of He. In this work, we perform systematical ab initio calculations to study the stability property of He in ZrCoH3 (ZrCo adsorbs the H isotope, forming ZrCoH3). The results suggest that the He atom will undergo displacements of 0.31 and 0.12 Å when it substitutes for Co and Zr, respectively. In contrast, the displacements are very large, at 0.67–1.09 Å, for He replacing H. Then, we introduce more than 20 alloying atoms in ZrCo to replace Co and Zr in order to examine the influence of alloying atoms on the stability of He at H sites. It is found that Ti, V, Cr, Mn, Fe, Zn, Nb, Mo, Tc, Ru, Ta, W, Re, and Os replacing Co can increase the substitution energy of H by the He closest to the alloying atom, whereas only Cr, Mn, Fe, Mo, Tc, Ru, Ta, W, Re, and Os replacing Co can increase the substitution energy of H by the He next closest to the alloying atom. The influence of the alloying atom substituting Zr site on the substitution energies is inconspicuous, and only Nb, Mo, Ru, Ta, and W increase the substitution energies of H by the He closest to the alloying atom. The increase in the substitution energy may suggest that these alloy atoms are conducive to fix the He atom in ZrCo and avoid the reduction in tritium purity.

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Effects of Mo substitution on the kinetic and thermodynamic characteristics of ZrCo1-xMox (x = 0–0.2) alloys for hydrogen storage

Cited by 17 publications

References 35 publications

Effects of V doping on microstructure, kinetic, and thermodynamic characteristics of Zr _{50‐
x} V _x Co ₅₀ ( x = 0, 2.5, 3.5, and 5.0) hydrogen storage alloys

Effects of V doping on microstructure, kinetic, and thermodynamic characteristics of Zr _{50‐
x} V _x Co ₅₀ ( x = 0, 2.5, 3.5, and 5.0) hydrogen storage alloys

Research Progress on the Anti-Disproportionation of the ZrCo Alloy by Element Substitution

Influence of Alloy Atoms on Substitution Properties of Hydrogen by Helium in ZrCoH3

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Effects of Mo substitution on the kinetic and thermodynamic characteristics of ZrCo1-xMox (x = 0–0.2) alloys for hydrogen storage

Cited by 17 publications

References 35 publications

Effects of V doping on microstructure, kinetic, and thermodynamic characteristics of Zr 50‐ x V x Co 50 ( x = 0, 2.5, 3.5, and 5.0) hydrogen storage alloys

Effects of V doping on microstructure, kinetic, and thermodynamic characteristics of Zr 50‐ x V x Co 50 ( x = 0, 2.5, 3.5, and 5.0) hydrogen storage alloys

Research Progress on the Anti-Disproportionation of the ZrCo Alloy by Element Substitution

Influence of Alloy Atoms on Substitution Properties of Hydrogen by Helium in ZrCoH3

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Product

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Effects of V doping on microstructure, kinetic, and thermodynamic characteristics of Zr _{50‐
x} V _x Co ₅₀ ( x = 0, 2.5, 3.5, and 5.0) hydrogen storage alloys

Effects of V doping on microstructure, kinetic, and thermodynamic characteristics of Zr _{50‐
x} V _x Co ₅₀ ( x = 0, 2.5, 3.5, and 5.0) hydrogen storage alloys