Systematical study on the roles of transition alloying substitutions on anti-disproportionation reaction of ZrCo during charging and releasing hydrogen

You, Yu-Wei; Yu, Jiangying; Yuan, Hui; Wu, Xue-Bing; Sun, Jingjing; Wang, Jinhua; Fang, Q.F.; Liu, C.S.

doi:10.1016/j.ijhydene.2020.03.107

Cited by 12 publications

(8 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Yang et al systematically investigated the influence of many alloying elements, such as Ti, Y, V, Nb, Ta, Cr, Mn, Ru, Rh, Pd, Zn, and Ni, on the anti-disproportionation ability of the ZrCo alloy, and they confirmed the ability of Ti, Nb, Ta, and V replacing Zr on the anti-disproportionation ability of ZrCo [13,14]. In our previous work, the effects of almost all transition alloying elements replacing Zr and Co on the anti-disproportionation of ZrCo were considered, and the results show that only Ni substituting for Co, and Fe, Co, Ni, Ru, Pd, Os, and Ir replacing Zr exhibited anti-disproportionation roles [32]. In the storage process of T in the form of hydride, many T atoms spontaneously decay into 3 He atoms, since the half life of T is approximately 12.3 years.…”

Section: Introductionsupporting

confidence: 69%

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

et al. 2021

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionsupporting

confidence: 69%

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

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…These first-principle calculations were performed with the density functional theory (DFT) as implemented in the Vienna Ab-initio Simulation Package (VASP). Through summarizing first-principle simulations [ 46 , 48 , 79 , 80 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 ], it has been shown that, in the ZrCo-H 2 system, the binding of H with Zr (or its substitute elements) shows a strong ion and weak covalence bond, and the binding of H with Co (or its substitute elements) shows a weak ion and strong covalence bond. In addition, the Zr-D distance in the 8e sites of ZrCoD 3 is smaller than the Zr-D distance of ZrD 2 [ 58 ].…”

Section: Effects Of Element Substitution On Anti-disproportionatiomentioning

confidence: 99%

“…The relationship between the size of the 8e site and the substitution atom can be seen from the simulation in Figure 5 b,d. The substitution of the Zr element is favorable for improving the anti-disproportionation of the ZrCo alloy, whereas the substitution from Co may not be suitable to enhance the anti-disproportionation [ 60 , 95 ]. Obviously, if the volume of the 8e site is small, it is hard for the H atom to diffuse into the 8e site, resulting in a significant decrease in the proportion of hydrogen atoms in the 8e site.…”

Section: Effects Of Element Substitution On Anti-disproportionatiomentioning

confidence: 99%

“… ( a ) Schematic diagram of H diffusion from the 8e site to the 4c 2 site in undoped, Ti-doped, and Hf-doped ZrCoH 3 ; ( b ) sizes of the 8e site in the undoped and doped ZrCoH 3 crystal; ( c ) the Zr–H (8e) bond length in the tetrahedron of undoped and doped ZrCoH 3 with the 8e site occupied by a H atom [ 60 ]; ( d ) volumes of the tetrahedron when one of the Zr/Co atoms in the tetrahedron is substituted by 3d, 4d, and 5d transition alloying solutes; ( e ) the bond lengths of Zr and H at the 8e site (at the center of the tetrahedron) when one of the Zr/Co atoms in the tetrahedron is substituted by 3d, 4d, and 5d transition alloying solutes [ 95 ]. …”

Section: Figurementioning

confidence: 99%

See 1 more Smart Citation

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

Wang

et al. 2020

Materials

View full text Add to dashboard Cite

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.

show abstract

“…In addition, element doping alters the microstructure inside the crystal including cell expansion/contraction, lattice distortion, and atom occupancy 16,30‐34 . Theoretically, H atoms tend to occupy the intertetrahedron space in ZrCoH 3 because the intertetrahedron space is larger than the interoctahedron space and the bond strength of Co‐H(T) is higher than that of Co‐H(O) 35 .…”

Section: Introductionmentioning

confidence: 99%

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

View full text Add to dashboard Cite

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.

show abstract

Systematical study on the roles of transition alloying substitutions on anti-disproportionation reaction of ZrCo during charging and releasing hydrogen

Cited by 12 publications

References 49 publications

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

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

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

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

Contact Info

Product

Resources

About

Systematical study on the roles of transition alloying substitutions on anti-disproportionation reaction of ZrCo during charging and releasing hydrogen

Cited by 12 publications

References 49 publications

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

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

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

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

Contact Info

Product

Resources

About

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