i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

A first-principles study of hydrogen storage of high

entropy alloy TiZrVMoNb

Jutao Hu a, Jinjing Zhang a, Haiyan Xiao a,*, Lei Xie b, Guangai Sun b,
Huahai Shen b,**, Pengcheng Li a, Jianwei Zhang a, Xiaotao Zu a
a
School of Physics, University of Electronic Science and Technology of China, Chengdu 610054, China
b
Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900, China

highlights graphical abstract

HEA TiZrVMoNb has a maximum

hydrogen storage capacity of
2.65 wt%.

A BCC to FCC phase transition oc-
curs when the hydrogen content
reaches to 1.5 wt%.

The thermal stability of HEA hy-
drides can be influenced by
hydrogen occupation.

The hydrogen storage property of
HEA TiZrVMoNb is superior to HEA
TiZrHfMoNb.

article info abstract

Article history: In this study, density functional theory calculations have been carried out to study the
Received 11 January 2021 hydrogen storage properties of high entropy alloy (HEA) TiZrVMoNb. It reveals that a
Received in revised form BCC/FCC phase transformation occurs when the hydrogen content reaches 1.5 wt%
7 March 2021 during hydrogenation process, and octahedral and tetrahedral interstitial sites are pref-
Accepted 24 March 2021 erable for hydrogen occupation before and after phase transformation, respectively.
Available online 28 April 2021 Further energetic analyses show that different hydrogen occupations in HEAs play an
important role in the thermal stability of hydrides. The maximum hydrogen storage ca-
Keywords: pacity for TiZrVMoNb is predicted to be 2.65 wt%, which is comparable to the largest value
First-principles calculations of 2.7 wt% for TiZrVHfNb and larger than that of other reported HEA hydrogen storage
High entropy alloys materials reported in the literature. As compared with the previously reported HEA
Hydrogen storage TiZrHfMoNb with the change of only one principal element, the TiZrVMoNb not only has
Site preference much higher hydrogen storage capacity, but also has more moderate hydrogen desorption
Phase transformation temperature. The difference in hydrogen storage properties between these two HEAs is
Phonon spectra mainly attributed to the atomic weight, site occupation, lattice distortion and chemical
effect of metal elements. The present study thus suggests that the TiZrVMoNb HEA has

* Corresponding author.
** Corresponding author.
E-mail addresses: hyxiao@uestc.edu.cn (H. Xiao), huahaishen@caep.cn (H. Shen).
https://doi.org/10.1016/j.ijhydene.2021.03.200
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8
great potential as hydrogen storage materials and proposes a strategy to enhance the
hydrogen storage properties of HEAs.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
Nowadays, due to the global energy crisis and environmental
pollution, it is necessary to develop alternative energy carrier
that is green and sustainable [1,2]. As a potential substitute for
conventional fossil fuels, hydrogen energy has attracted
special attention because it is clean, non-toxic, renewable,
abundant and superior gravimetric energy density when
compared to any known fuel [3,4]. Besides the production of
hydrogen using renewable energies, hydrogen storage has
been playing a vital role in developing the hydrogen-based
energy system, and material-based storage would be an op-
tion for the effective and stable storage/transportation of the
hydrogen [5e10].
High entropy alloy (HEA), which is composed of five or
more metal elements with atomic concentrations between 5
and 35 at.% [11e19], is a new concept in the field of materials-
based hydrogen storage. In the past few years, several efforts
have been made in the development of HEAs for hydrogen
storage. Kao et al. [20] synthesized CoFeMnTixVyZrz HEA and
found that the hydrogen storage capacity can be optimized by
adjusting Ti, V, and Zr contents. Sahlberg et al. [21] have re-
ported that the Body Centered Cubic (BCC) TiZrVHfNb HEA has
a superior high hydrogen storage capacity of 2.7 wt% at 299  C.
Shen et al. [22] found that the HEA TiZrHfMoNb possesses the
possibility of a reversible storage during the hydrogen
absorption-desorption cycles. Nygård et al. [23] reported that
TiVCrNb exhibits a rapid hydrogen absorption kinetics with a
hydrogen storage capacity of 1.96 wt%, and the hydrogen ab-
sorption of this HEA is not dependent on any elaborate acti-
vation procedure. In a recent study, Edalati et al. [24] designed
a new HEA TiZrCrMnFeNi, which can absorb and desorb 1.7 wt
% of hydrogen at room temperature with a fast kinetics and
without any activation treatment. In spite of these in-
vestigations, the study on the hydrogen storage of HEAs is still
in its infancy thus far. To achieve practical application, it is a
long way to solve problems like great weight, low storage ca-
pacity, slow absorption and desorption kinetics, and so on.
However, considering the endless possibility to explore the
compositional space of HEAs, designing HEAs with light
weight and high hydrogen storage capacity for practical
application is still possible.
Thus far, although a number of investigations have been
carried out on the hydrogen storage properties of HEAs, the
underlying mechanism for hydrogenation of HEAs still re-
mains unclear. Zepon et al. [25] suggested that during hy-
drogenation process of HEA MgZrTiFe0.5Co0.5Ni0.5, the
hydrogen atoms occupy octahedral sites (O-sites) of BCC
structure at first, and then occupy tetrahedral sites (T-sites) of
FCC structure which is transformed from BCC structure.
Zlotea et al. [26] reported that the hydrogen absorption of HEA
21051
TiZrHfTaNb induces a two-phase transformation from initial
BCC to Body Centered Tetragonal (BCT) monohydride at very
low pressure and finally to a dihydride phase with FCC
structure. They thus suggested that hydrogen atoms prefer-
entially occupy the O-sites of BCT structure (monohydride)
and the T-sites of FCC structure (dihydride). Sahlberg et al.
[21] proposed that the large hydrogen storage capacity of HEA
TiZrVHfNb is originated from the lattice strain in the alloy
that makes it favorable to absorb hydrogen in both T-sites
and O-sites. Karlsson et al. [27] studied the hydrogenation
mechanism in HEA TiZrVHfNb by in-situ and ex-situ neutron
diffraction experiments. They found that the hydrogen
occupation of T-sites to O-sites is 53:47 at high temperature of
500  C, and the ratio changes to 92.9:5.2 at room temperature.
Obviously, there still remains a debate on the site occupation
for hydrogen atoms in the HEAs. Thus, a detailed theoretical
investigation of site preference for hydrogen atoms combined
with phase transformation in hydrogen absorption of HEAs is
necessary to gain more fundamental insights into hydrogen
storage of the HEAs.
In this paper, first-principles calculations based on density
functional theory (DFT) are carried out to investigate the
hydrogen absorption behavior in HEA TiZrVMoNb. The site
occupation of hydrogen atoms, hydrogen absorption induced
phase transformation, threshold hydrogen content for phase
transformation and the maximum hydrogen storage capacity
are all determined. A comparison of hydrogen storage prop-
erties between TiZrVMoNb and TiZrHfMoNb [28] that are re-
ported recently has been made and the origin of the
differences has been explored. Besides, the effect of complete
substitution of Hf for V on the hydrogen storage properties of
HEAs has also been discussed.
Computational details
All the DFT calculations are performed using the Vienna Ab
Initio Simulation Package (VASP) [29e31], with spin-polarized
effects considered. The interaction between ions and elec-
trons is described using the projector augment wave (PAW)
[32] method, and the exchange-correlation effects are treated
using the functional of Perdew-Burke-Ernzerhof (PBE) [33]
under the generalized gradient approximation (GGA) [34]. The
kinetic-energy cutoff is set to be 650 eV and a 2  2  2
Monkhorst-Pack k-point mesh is employed. The convergence
criteria for total energies and forces are 1  104 eV/atom and
-1  103 eV/
A, respectively. In this study, the HEA TiZrVMoNb
consists of five metal elements in equal atomic ratio, meaning
that the number of atoms in the HEA model should be a
multiple of five. In order to make a compromise between
computational accuracy and computational efficiency, a
3  5  2 BCC supercell consisting of 60 atoms is used for HEA
21052 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8
TiZrVMoNb, as illustrated in Fig. 1. The structural models of
TiZrVMoNb and its hydrides are built by a randomization
method as described previously [28]. The lattice constant of
TiZrVMoNb is determined to be 3.26
A, agreeing well with the
experimental value of 3.25
A [35]. As for HEA TiZrVMoNb hy-
drides, 3  5  2 and 3  5  1 supercells consisting of 60 metal
atoms are used for BCC and FCC phases, respectively, and
hydrogen atoms occupying O-sites and T-sites are considered
in both cases.
Results and discussions
Hydrogen absorption in BCC phase of TiZrVMoNb
To determine the thermal stability of the TiZrVMoNb
hydrides, the binding energy (EB) between hydrogen and alloys
h i
is calculated by EB ¼ n1 Etot ðMÞ þn2 EðH2 Þ Etot ðMHn Þ [36,37],
where Etot ðMÞ is the total energy of HEA TiZrVMoNb without
hydrogen, EðH2 Þ is the total energy of an isolated H2 molecule,
and Etot ðMHn Þ is the total energy of the TiZrVMoNb with n
hydrogen atoms per formula unit. The binding energies for
TiZrVMoNb hydrides with hydrogen atoms occupying O-sites
and T-sites are plotted in Fig. 2. Here, a positive binding energy
means that HEA TiZrVMoNb are capable of accommodating
hydrogen atoms. Also, the larger the binding energy, the
stronger the interaction between hydrogen and HEA TiZrV-
MoNb [38].
As shown in Fig. 2, O-site occupation is energetically
favorable relative to T-site occupation for BCC TiZrVMoNb
hydrides. Experimentally, Zepon et al. also observed that
hydrogen atoms prefer to occupy the O-sites over T-sites in
the BCC MgZrTiFe0.5Co0.5Ni0.5 [25]. It is noticeable that the site
Fig. 1 e Schematic view of the geometrical structure of BCC
TiZrVMoNb. The purple, green, red, yellow and pink
spheres represent Ti, Zr, V, Mo and Nb atoms, respectively.
(For interpretation of the references to color in this figure
legend, the reader is referred to the Web version of this
article.)
Fig. 2 e The calculated binding energy as a function of
hydrogen content for BCC TiZrVMoNb hydrides. The BCC-O
and BCC-T represent BCC TiZrVMoNb hydrides with
hydrogen atoms occupying octahedral and tetrahedral
sites, respectively.
preference of hydrogen in high entropy alloy is different from
that in pure BCC transition metals, such as V, Nb and Mo,
where the T-sites are favorable positions for hydrogen occu-
pation [39,40]. In addition, the binding energy decreases with
the increasing hydrogen content for both O-site and T-site
occupation, which indicates that there is a decline in the
interaction between hydrogen atoms and BCC TiZrVMoNb
and a phase transformation may occur when hydrogen con-
tent reaches a certain level. Similar trend in the binding en-
ergies with increasing hydrogen content has also been
observed by Yuan et al. [41] for cubic YFe2 and by Hu et al. [37]
for HEA TiZrHfScMo.
Hydrogen absorption in FCC phase of TiZrVMoNb
The absorption of hydrogen into a host material for storage
purpose is often accompanied by phase transformation [42].
Experimentally, the HEAs such as MgZrTiFe0.5Co0.5Ni0.5 [25],
TiZrHfMoNb [22], TiVNbHf [23], TiZrHfTaNb [26] and TiZrVNb
[43] all have been observed to undergo BCC/FCC phase
transformation during hydrogenation. Nygård et al. [23] have
investigated the hydrogen storage properties for a series of
quaternary and quinary HEAs and proposed that under the
condition of valence electron concentration (VEC)  4.75 the
hydrides assume a FCC/BCC multiphase composition and the
amount of FCC in the multiphase decreases with the
increasing VEC. In this study, the VEC for HEA TiZrVMoNb is
PN
determined to be 4.8 based onVEC ¼ ci ðVECÞi , where ci and
i¼1
ðVECÞi are the atomic fraction and the VEC for the i-th element,
respectively, and N is the number of elements [44]. Consid-
ering that the VEC for TiZrVMoNb HEA is close to the threshold
and the binding energies for its BCC hydrides decreases with
the increasing hydrogen content, the possibility of BCC/FCC
phase transformation during hydrogen absorption is thus
explored.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8 21053

The site preference for hydrogen occupation in FCC phase

is firstly investigated. Fig. 3 presents the binding energies for
O-site and T-site occupation in FCC phase. When the
hydrogen content is smaller than 0.66 wt%, the FCC hydride is
found to be thermally unstable for both O-site and T-site
occupation. The O-site occupation is shown to be preferable to
T-site occupation when the hydrogen content increases to
0.88 wt%, above which the site preference inverses. As shown
in Fig. 3, the binding energy for T-site occupation increases
with the increasing hydrogen content, indicating that the
interaction between hydrogen atoms and FCC TiZrVMoNb
becomes stronger. It is noted that the binding energies in BCC
and FCC phases decrease and increase with the increasing
hydrogen content, respectively. Thus, a BCC/FCC phase
transformation is expected to occur when the hydrogen con-
tent reaches a certain level.
The energy differences between FCC and BCC TiZrVMoNb Fig. 4 e The energy difference between FCC and BCC
hydrides are presented in Fig. 4, where hydrogen atoms TiZrVMoNb hydrides (DE ¼ EFCC-EBCC) as a function of
occupy octahedral sites in BCC phase. As for FCC phase, the hydrogen content.
hydrogen atoms occupy octahedral and tetrahedral sites
when the hydrogen content is smaller and larger than 0.88 wt
%, respectively. Obviously, a BCC/FCC phase transformation in the TiZrHfMoNb alloys, which is confirmed by density
occurs when hydrogen content reaches about 1.5 wt%. It is functional theory calculations of Hu et al. [28]. Among a series
noted that the threshold hydrogen content (1.5 wt%) of phase of quaternary and quinary HEAs investigated by Nygård et al.
transformation is larger than the value of 0.88 wt% for site [20], the TiZrVHfNb, TiZrVNb, TiVNbHf, TiVNbTa and TiVCrNb
preference transition in FCC phase, which means that after are also observed to undergo BCC/FCC phase transformation
TiZrVMoNb hydrides transform into FCC phase, the T-sites are in the hydrogenation process.
preferable for hydrogen atoms to occupy. Therefore, hydrogen
atoms prefer to occupy O-sites and T-sites in BCC and The maximum hydrogen storage capacity of TiZrVMoNb
FCC TiZrVMoNb, respectively. Our results are consistent with
the investigation of hydrogen storage behavior of HEA To investigate the maximum hydrogen storage capacity of
MgZrTiFe0.5Co0.5Ni0.5 by Zepon et al. [25], who suggested that HEA TiZrVMoNb, the binding energy and the formation
hydrogen atoms occupy O-sites in the original BCC structure enthalpy (Hform) as a function of hydrogen content are
and T-sites in the corresponding FCC hydride. Zlotea et al. [26] further calculated, as presented in Fig. 5. Considering that
studied the hydrogen storage properties of single-phase BCC hydrogen atoms prefer T-sites to O-sites in FCC phase, we
TiZrHfTaNb and found that this HEA finally transforms into first increase the number of T-site occupation. After all the
an FCC dihydride after hydrogen absorption. Shen et al. [22] T-sites are occupied in FCC phase, corresponding to a
observed a reversible BCC/FCC single-phase transformation hydrogen content of 2.59 wt%, O-site occupations are also

Fig. 5 e The calculated binding energy and formation

Fig. 3 e The calculated binding energy as a function of enthalpy as a function of hydrogen content for the FCC
hydrogen content for FCC TiZrVMoNb hydrides. The FCC-O TiZrVMoNb hydrides. The T and O represent hydrogen
and FCC-T represent hydrogen occupying octahedral and occupying tetrahedral and octahedral sites in FCC
tetrahedral sites in FCC TiZrVMoNb hydrides, respectively. TiZrVMoNb hydrides, respectively.
21054 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8
taken into account. The formation enthalpy is determined
h i
Etot ðMHn ÞEðTiÞEðZrÞEðVÞEðMoÞEðNbÞn2 EðH2 Þ
by Hform ¼ N [45]. Here,
Etot ðMHn Þ is the total energy of TiZrVMoNb with n hydrogen
atoms per formula unit, N is the number of atoms in the unit
cell, EðH2 Þ is the total energy of an isolated H2 moleculeEðTiÞ,
EðZrÞ EðVÞ, EðMoÞ and EðNbÞ are the single atomic energies of
the pure elements in their respective stable solid states. The
negative Hform means that accommodation of hydrogen
atoms is an exothermic process. As shown in Fig. 5, the
binding energies and formation enthalpies of all the
considered FCC TiZrVMoNb hydrides are positive and
negative, respectively, suggesting that when the hydrogen
content ranges from 1.5 to 3.84 wt%, the hydrides are ener-
getically stable. Furthermore, the binding energy increases
first and then decreases with the increasing hydrogen con-
tent. Meanwhile, an opposite trend is observed for formation
enthalpy. When the hydrogen content reaches 2.59 wt%,
corresponding to all T-sites occupation, a maximum and
minimum value occur for binding energy and formation
enthalpy, respectively. Hence, it can be concluded that the
occupation of hydrogen atoms in T-site can enhance the
thermal stability of FCC HEA hydride, and additional O-site
occupations would destabilize the hydride. This result also
verifies the conclusion that the hydrogen prefers to occupy
T-site in FCC phase as discussed above.
Furthermore, we calculate the phonon spectra of a series of
HEA TiZrVMoNb hydrides by employing Phonopy code [28] to
study their lattice dynamical stabilities. All the T-sites are
occupied in each case and the O-site occupation ratios are 0%,
5%, 10% and 50%, corresponding to hydrogen content of
2.59 wt%, 2.65 wt%, 2.71 wt% and 3.22 wt%, respectively. For
HEA TiZrVMoNb hydrides with the hydrogen content of
2.59 wt% and 2.65 wt%, one can see from Fig. 6 that all the
phonon frequencies are positive, meaning that these two
hydrides are lattice dynamically stable. When the hydrogen
content is larger than 2.65 wt%, i.e., O-site occupation exceeds
5%, imaginary frequencies appear and the hydrides are not
stable dynamically any more. Hence, the maximum hydrogen
storage capacity of TiZrVMoNb is suggested to be 2.65 wt%,
corresponding to a hydrogen-to-metal ratio (H/M) of 2.05,
which is comparable to the largest value of 2.7 wt% for
TiZrVHfNb [21] reported in the literature and larger than those
for most reported HEA hydrogen storage materials like
Fig. 6 e Phonon spectra of TiZrVMoNb hydrides with the hydrogen content of (a) 2.59 wt% and (b) 2.65 wt%.
TiZrHfTaNb (1.68 wt%) [26], TiZrNbTa (1.6 wt%) [46] and
MgZrTiFe0.5Co0.5Ni0.5 (1.2 wt%) [25].
To further explore the variation of electronic structures of
HEA TiZrVMoNb during the hydrogenation process, the
density of state (DOS) distribution of TiZrVMoNb and its
hydrides are analyzed. The total DOS of BCC TiZrVMoNb,
BCC TiZrVMoNbH1.5, FCC TiZrVMoNbH7.5 and FCC
TiZrVMoNbH10.25 are plotted in Fig. 7. It can be seen that
TiZrVMoNb and its hydrides are metallic with no band
gap, which is consistent with other alloy hydrogen stor-
age materials [37,47]. Furthermore, BCC TiZrVMoNb and
TiZrVMoNbH1.5 exhibit similar electronic structures, which
are totally different from those of FCC TiZrVMoNbH7.5 and
TiZrVMoNbH10.25. In Fig. 7(c) and (d), it can be seen that the
orbitals are more delocalized in the FCC phases than those in
BCC phases. Züttel [5] suggested that the electronic struc-
tures of alloy hydrogen storage materials change before and
after the phase transformation during the hydrogenation
process, which is mainly attributed to the different crystal
structure of the metal lattice. Therefore, the difference in the
electronic structures of TiZrHfMoNb hydrides before and
after phase transformation may originate from the differ-
ence between BCC and FCC structure.
A comparison of hydrogen storage property between
TiZrVMoNb and TiZrHfMoNb
In our recent work, the hydrogen storage properties of BCC
HEA TiZrHfMoNb have been reported [28]. This alloy also
shows a BCC to FCC phase transformation during the hy-
drogenation process and exhibits a similar site preference as
compared with TiZrVMoNb. However, it is unexpected that
the hydrogen storage properties of these two high entropy
alloys are quite different from each other with the change of
only one principal element. The maximum hydrogen storage
capacity of TiZrHfMoNb is predicted to be 1.94 wt% [24],
which is much smaller than the value of 2.65 wt% for
TiZrVMoNb HEA investigated in this study. The enhanced
hydrogen storage capacity for TiZrVMoNb can be mainly
attributed to the following two aspects. First, the mass of
TiZrVMoNb is lighter than that of TiZrHfMoNb due to the
small atomic weight of V (50.94). Another additional impor-
tant aspect is that the HEA TiZrVMoNb can not only have all
the T-sites being occupied by hydrogen, but also have 5% O-
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8 21055

Fig. 7 e The total density of state for (a) BCC TiZrVMoNb; (b) BCC TiZrVMoNbH1.5; (c) FCC TiZrVMoNbH7.5; (d) FCC
TiZrVMoNbH10.25. The Fermi level is located at 0 eV.

sites occupation simultaneously. This is different from the redistribution in HEAs. Fig. 9 (a) and (b) present the electron
case of TiZrHfMoNb, in which only T-sites are occupied by localization function (ELF) image of the (001) plane for HEAs
hydrogen atoms. Actually, the different site occupation can TiZrVMoNb and TiZrHfMoNb, respectively. As compared
be considered as a result of the different interaction between with the homogeneous distribution of electrons in pure BCC
hydrogen and metal atoms, due to elastic effect and chemi- transition metals like Mo [40], the electrons in HEA are
cal effect [48]. On one hand, the lattice distortion of TiZrV-
MoNb (6.84%) is larger than that of TiZrHfMoNb (6.1%), i.e.,
the symmetry of interstitial sites in TiZrVMoNb is lowered
more significantly, as shown in Fig. 8, which leads to some O-
sites being occupied by hydrogen atoms. On the other hand,
the substitution of Hf for V would result in electron

Fig. 8 e Schematic view of the lattice distortion in FCC
TiZrVMoNb lattice. The distorted octahedral sites are
indicted by blue dot lines. (For interpretation of the
references to color in this figure legend, the reader is
referred to the Web version of this article.)
Fig. 9 e Electron localization function (ELF) image of the
(001) plane for HEAs (a) TiZrVMoNb and (b) TiZrHfMoNb.
The rectangles are used to highlight the different electron
distribution in the same region of TiZrVMoNb and
TiZrHfMoNb.
21056 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8

distributed in-homogeneously, because the surrounding

chemical environments over interstitial sites in HEAs are
variable and complex due to the random distribution of the
multi-principle metal atoms. Furthermore, the distribution
of electrons in TiZrVMoNb is more localized than that in
TiZrHfMoNb. Ravindran et al. [49] and Vajeeston et al. [50]
proposed that hydrogen prefers to stay at the region with
more localized electrons in metal matrices. Thus, the
enhanced electron localization in TiZrVMoNb should be
another critical variable to influence the O-site occupation.
Lee et al. [51] investigated the alloying of Fe, Ni, Al, Ti, and Nb
in V by first-principles calculations, and demonstrated that
the stability of interstitial sites in alloys can be influenced by
the nearby metal elements. Kong et al. [52] investigated the
interaction between transition metal solutes and hydrogen
in tungsten by first-principles calculation. They found that
the site occupation of hydrogen in tungsten can be signifi-
cantly influenced by the solute atoms, which is consistent
with our results.
Comparing the binding energy of HEA hydrides, we find
that the binding energy of FCC TiZrVMoNb hydrides is lower
than that of TiZrHfMoNb hydrides [28], meaning that the
thermal stability of TiZrVMoNb hydrides is lower [53]. Nygård
et al. [23] proposed that the thermal stability of HEA hydrides
decrease linearly with increasing VEC. The VEC of TiZrVMoNb
and TiZrHfMoNb are 4.8 and 4.6, respectively, i.e. the hydrides
of TiZrVMoNb have lower thermal stability as compared with
TiZrHfMoNb, which is consistent with the results of binding
energy calculation. For TiZrHfMoNb, the binding energy of the
saturated hydride (H/M ¼ 2) is 1.12 eV/atom. In the case of
TiZrVMoNb, the binding energy for the saturated hydride (H/
M ¼ 2.05) is only 0.44 eV/atom, which is slightly larger than the
binding energy values of 0.21e0.42 eV for ideal hydrogen
storage materials [54], suggesting that the TiZrVMoNb HEA is a
good candidate material for hydrogen storage. To further
explore the origin of the thermal stability difference between
FCC TiZrVMoNb and TiZrHfMoNb hydrides, Bader charge an-
alyses are performed. If the value of the Bader charge is posi-
tive, it means electron loss for this element after bonding,
while a negative value implies electron gain [37]. The larger the
negative (or positive) value of the charge for an element, the
stronger its ability to gain (or lose) electrons. As can be seen
from Fig. 10, all the metal atoms lose electrons, while the H
atoms gain electrons in both TiZrVMoNb and TiZrHfMoNb
hydrides, because the electronegativity of H (2.2) is the stron-
gest among all the elements in the investigated systems [55]. It
can also be observed that the substitution of Hf for V leads to
charge redistribution in the system. The Bader charge of V in
TiZrVMoNb is significantly lower than the counterpart in
TiZrHfMoNb with a charge difference of 0.405 |e|. Since the
electronegativity of V (1.63) is larger than that of Hf (1.3) [56],
the V element exhibits a weaker ability to lose electrons.
Consequently, the strength of the bond between hydrogen and
metal elements is weakened and the thermal stability of the
TiZrVMoNb hydride is reduced. Similar phenomenon has been
observed by Khatabi et al. [55], who found that doping transi-
tion metal elements with larger electronegativity into MgH2
can decrease the thermal stability of system, agreeing well
with our results. It is noticeable that the hydrogen occupation
sites in HEAs also affect their thermal stability. In both
Fig. 10 e Average Bader charge (|e|) of hydrogen and metal
elements in FCC TiZrVMoNb and TiZrHfMoNb hydrides
with H/M ratio of 2.
TiZrVMoNb and TiZrHfMoNb the T-sites can be fully occupied
by hydrogen atoms, but O-sites can only be occupied in
TiZrVMoNb, which would further decrease the binding energy
as shown in Fig. 5. These results suggest that the hydrogen
desorption temperature in TiZrVMoNb will be lower than that
in TiZrHfMoNb. In addition, the variables to determine the
hydrogen storage properties of HEAs become much more than
those in traditional alloys, which may open up more possibil-
ities for designing HEAs with superior hydrogen storage.
Conclusion
In this work, the hydrogen storage properties of HEA TiZrV-
MoNb have been investigated by a density functional theory
method. The calculations show that a BCC to FCC phase
transformation occurs when the hydrogen content reaches
1.5 wt% and hydrogen prefers to occupy the octahedral and
tetrahedral sites in BCC and FCC phase, respectively. Further
binding energy and formation enthalpy calculations indicate
that hydrogen occupation at tetrahedral sites can enhance the
thermal stability of FCC HEA hydride, while additional octa-
hedral site occupation would destabilize the hydride. The
maximum hydrogen storage capacity is predicted to be 2.65 wt
%, corresponding to an H/M ratio of 2.05. In comparison to our
previous reported HEA TiZrHfMoNb, the substitution of Hf for
V in HEA enhances the hydrogen storage capacity and de-
creases the thermal stability of hydrides simultaneously,
which can be attributed to the small atomic weight of V,
different site occupation, large lattice distortion as well as
charge redistribution in HEA TiZrVMoNb. The presented re-
sults suggest that TiZrVMoNb HEA is a promising candidate
for hydrogen storage and may pave the way for designing new
high entropy alloy for hydrogen storage.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8
Acknowledgements
Haiyan Xiao was supported by the Joint Funds of the National
Natural Science Foundation of China (Grant No. U1930120).
Huahai Shen was supported by the President Foundation of
the China Academy of Engineering Physics (Grant No.
YZJJLX2018003) and the National Natural Science Foundation of
China (Grant No. 21601168). The theoretical calculations were
performed using the supercomputer resources at TianHe-1
located at National Supercomputer Center in Tianjin.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.03.200.
references
[1] Jain IP. 21st Century’s energy: hydrogen energy system. Int J
Hydrogen Energy 2009;34(17):7368e78.
[2] Abdalla AM, Hossain S, Nisfindy OB, Azad AT, Dawood M,
Azad AK. Hydrogen production, storage, transportation and
key challenges with applications: a review. Energy Convers
Manag 2018;165:602e27.
[3] Abe JO, Popoola API, Ajenifuja E, Popoola OM. Hydrogen
energy, economy and storage: review and recommendation.
Int J Hydrogen Energy 2019;44(29):15072e86.
[4] Dunn S. Hydrogen futures: toward a sustainable energy
system. Int J Hydrogen Energy 2002;27(3):235e64.
[5] Züttel A. Materials for hydrogen storage. Mater Today
2003;6(9):24e33.
[6] von Colbe JB, Ares JR, Barale J, Baricco M, Buckley C,
Capurso G, Gallandat N, Grant DM, Guzik MN, Jacob I,
Jensen EH, Jensen T, Jepsen J, Klassen T, Lototskyy MV,
Manickam K, Montone A, Puszkiel J, Sartori S, Sheppard DA,
Stuart A, Walker G, Webb CJ, Yang H, Yartys V, Zuttel A,
Dornheim M. Application of hydrides in hydrogen storage
and compression: achievements, outlook and perspectives.
Int J Hydrogen Energy 2019;44(15):7780e808.
[7] Sreedhar I, Kamani KM, Kamani BM, Reddy BM, Venugopal A.
A Bird’s Eye view on process and engineering aspects of
hydrogen storage. Renew Sustain Energy Rev 2018;91:838e60.
[8] Sakintuna B, Lamari-Darkrim F, Hirscher M. Metal hydride
materials for solid hydrogen storage: a review. Int J Hydrogen
Energy 2007;32(9):1121e40.
[9] Rusman NAA, Dahari M. A review on the current progress of
metal hydrides material for solid-state hydrogen storage
applications. Int J Hydrogen Energy 2016;41(28):12108e26.
[10] Ren JW, Musyoka NM, Langmi HW, Mathe M, Liao SJ. Current
research trends and perspectives on materials-based
hydrogen storage solutions: a critical review. Int J Hydrogen
Energy 2017;42(1):289e311.
[11] Yeh JW, Chen SK, Lin SJ, Gan JY, Chin TS, Shun TT, Tsau CH,
Chang SY. Nanostructured high-entropy alloys with multiple
principal elements: novel alloy design concepts and
outcomes. Adv Eng Mater 2004;6(5):299e303.
[12] Ye YF, Wang Q, Lu J, Liu CT, Yang Y. High-entropy alloy:
challenges and prospects. Mater Today 2016;19(6):349e62.
[13] Lu CY, Niu LL, Chen NJ, Jin K, Yang TN, Xiu PY, Zhang YW,
Gao F, Bei HB, Shi S, He MR, Robertson IM, Weber WJ,
Wang LM. Enhancing radiation tolerance by controlling
21057
defect mobility and migration pathways in multicomponent
single-phase alloys. Nat Commun 2016;7:8.
[14] Zheng Y, Jia N, Qian F, Wang J, Xue Y, Jin K. Thermal stability
of (CoCrFeNi)94Ti2Al4 alloy containing coherent
nanoprecipitates at intermediate temperatures. Materialia
2020;12:100775.
[15] Liu X, Sha G, Wu QL, Liang YJ, Huang JT, Jin K, Xue YF,
Wang BP, Wang LJ, Wang L, Wang FC, Fan QB, Xia ZH. Phase
stability of an high-entropy Al-Cr-Fe-Ni-V alloy with
exceptional mechanical properties: first-principles and APT
investigations. Comput Mater Sci 2019;170:9.
[16] Lin YP, Yang TF, Lang L, Shan C, Deng HQ, Hu WY, Gao F.
Enhanced radiation tolerance of the Ni-Co-Cr-Fe high-
entropy alloy as revealed from primary damage. Acta Mater
2020;196:133e43.
[17] Zhang YW, Wang X, Osetsky YN, Tong Y, Harrison R,
Donnelly SE, Chen D, Wang YQ, Bei HB, Sales BC, More KL,
Xiu PY, Wang LM, Weber WJ. Effects of 3d electron
configurations on helium bubble formation and void
swelling in concentrated solid-solution alloys. Acta Mater
2019;181:519e29.
[18] Li XQ, Li W, Irving DL, Varga LK, Vitos L, Schonecker S.
Ductile and brittle crack-tip response in equimolar refractory
high-entropy alloys. Acta Mater 2020;189:174e87.
[19] Li XQ, Wei DX, Vitos L, Lizarraga R. Micro-mechanical
properties of new alternative binders for cemented carbides:
CoCrFeNiWx high-entropy alloys. J Alloys Compd 2020;820:8.
[20] Kao YF, Chen SK, Sheu JH, Lin JT, Lin WE, Yeh JW, Lin SJ,
Liou TH, Wang CW. Hydrogen storage properties of multi-
principal-component CoFeMnTixVyZrz alloys. Int J Hydrogen
Energy 2010;35(17):9046e59.
[21] Sahlberg M, Karlsson D, Zlotea C, Jansson U. Superior
hydrogen storage in high entropy alloys. Sci Rep
2016;6:36770.
[22] Shen HH, Zhang JW, Hu JT, Zhang JC, Mao YW, Xiao HY,
Zhou XS, Zu XT. A novel TiZrHfMoNb high-entropy alloy for
solar thermal energy storage. Nanomaterials 2019;9(2):248.
[23] Nygård MM, Ek G, Karlsson D, Sorby MH, Sahlberg M,
Hauback BC. Counting electrons - a new approach to tailor
the hydrogen sorption properties of high-entropy alloys.
Acta Mater 2019;175:121e9.
[24] Edalati P, Floriano R, Mohammadi A, Li YT, Zepon G, Li HW,
Edalati K. Reversible room temperature hydrogen storage in
high-entropy alloy TiZrCrMnFeNi. Scripta Mater
2020;178:387e90.
[25] Zepon G, Leiva DR, Strozi RB, Bedoch A, Figueroa SJA,
Ishikawa TT, Botta WJ. Hydrogen-induced phase transition
of MgZrTiFe0.5Co0.5Ni0.5 high entropy alloy. Int J Hydrogen
Energy 2018;43(3):1702e8.
[26] Zlotea C, Sow MA, Ek G, Couzinie JP, Perriere L, Guillot I,
Bourgon J, Moller KT, Jensen TR, Akiba E, Sahlberg M.
Hydrogen sorption in TiZrNbHfTa high entropy alloy. J Alloys
Compd 2019;775:667e74.
[27] Karlsson D, Ek G, Cedervall J, Zlotea C, Moller KT, Hansen TC,
Bednarcik J, Paskevicius M, Sorby MH, Jensen TR, Jansson U,
Sahlberg M. Structure and hydrogenation properties of a
HfNbTiVZr high-entropy alloy. Inorg Chem
2018;57(4):2103e10.
[28] Hu J, Zhang J, Xiao H, Xie L, Shen H, Li P, Zhang J, Gong H,
Zu X. A density functional theory study of the hydrogen
absorption in high entropy alloy TiZrHfMoNb. Inorg Chem
2020;59(14):9774e82.
[29] Kresse G, Joubert D. From ultrasoft pseudopotentials to the
projector augmented-wave method. Phys Rev B
1999;59(3):1758e75.
[30] Kresse G, Furthmuller J. Efficiency of ab-initio total energy
calculations for metals and semiconductors using a plane-
wave basis set. Comput Mater Sci 1996;6(1):15e50.
21058 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 2 1 0 5 0 e2 1 0 5 8
[31] Kresse G, Furthmuller J. Efficient iterative schemes for ab
initio total-energy calculations using a plane-wave basis set.
Phys Rev B 1996;54(16):11169e86.
€ chl PE. Project augmented-wave method. Phys Rev B
[32] Blo
1994;50(24):17953e79.
[33] Perdew JP, Burke K, Ernzerhof M. Generalized gradient
approximation made simple. Phys Rev Lett
1996;77(18):3865e8.
[34] White JA, Bird DM. Implementation of gradient-corrected
exchange-correlation potentials in Car-Parrinello total-
energy calculations. Phys Rev B 1994;50(7):4954e7.
[35] Kunce I, Polanski M, Bystrzycki J. Microstructure and
hydrogen storage properties of a TiZrNbMoV high entropy
alloy synthesized using Laser Engineered Net Shaping
(LENS). Int J Hydrogen Energy 2014;39(18):9904e10.
[36] Gesari SB, Pronsato ME, Visintin A, Juan A. Hydrogen storage
in AB(2) laves phase (A ¼ Zr, Ti; B ¼ Ni, Mn, Cr, V): binding
energy and electronic structure. J Phys Chem C
2010;114(39):16832e6.
[37] Hu JT, Shen HH, Jiang M, Gong HF, Xiao HY, Liu ZJ, Sun GA,
Zu XT. A DFT study of hydrogen storage in high-entropy
alloy TiZrHfScMo. Nanomaterials 2019;9(3):461.
[38] Shevlin SA, Guo ZX. Density functional theory simulations of
complex hydride and carbon-based hydrogen storage
materials. Chem Soc Rev 2009;38(1):211e25.
[39] Hauck J, Schenk HJ. Coordination of hydrogen in transition-
metal hydrides. J Less Common Met 1977;51(2):251e8.
[40] Duan C, Liu YL, Zhou HB, Zhang Y, Jin S, Lu GH, Luo GN.
First-principles study on dissolution and diffusion
properties of hydrogen in molybdenum. J Nucl Mater
2010;404(2):109e15.
[41] Yuan SR, Ouyang LZ, Zhu M, Zhao YJ. Theoretical study of
YFe2Hx(x¼0-5): a comparison between cubic and
orthorhombic phases. J Magn Magn Mater 2018;460:61e8.
[42] Schlapbach L, Zuttel A. Hydrogen-storage materials for
mobile applications. Nature 2001;414(6861):353e8.
[43] Nygård MM, Ek G, Karlsson D, Sahlberg M, Sorby MH,
Hauback BC. Hydrogen storage in high-entropy alloys with
varying degree of local lattice strain. Int J Hydrogen Energy
2019;44(55):29140e9.
[44] Guo S, Ng C, Lu J, Liu CT. Effect of valence electron
concentration on stability of fcc or bcc phase in high entropy
alloys. J Appl Phys 2011;109(10):103505.
[45] Wolverton C, Ozolins V. First-principles aluminum database:
energetics of binary Al alloys and compounds. Phys Rev B
2006;73(14):144104.
[46] Zhang C, Song AN, Yuan Y, Wu Y, Zhang PL, Lu ZP, Song XP.
Study on the hydrogen storage properties of a TiZrNbTa high
entropy alloy. Int J Hydrogen Energy 2020;45(8):5367e74.
[47] van Midden HJP, Prodan A, Zupanic E, Zitko R, Makridis SS,
Stubos AK. Structural and electronic properties of the
hydrogenated ZrCr2 laves phases. J Phys Chem C
2010;114(9):4221e7.
[48] Myers SM, Baskes MI, Birnbaum HK, Corbett JW, Deleo GG,
Estreicher SK, Haller EE, Jena P, Johnson NM, Kirchheim R,
Pearton SJ, Stavola MJ. Hydrogen interactions with defects in
crystalline solids. Rev Mod Phys 1992;64(2):559e617.
[49] Ravindran P, Vajeeston P, Vidya R, Fjellvag H, Kjekshus A.
Modeling of hydrogen storage materials by density-
functional calculations. J Power Sources 2006;159(1):88e99.
[50] Vajeeston P, Ravindran P, Vidya R, Kjekshus A, Fjellvag H.
Site preference of hydrogen in metal, alloy, and intermetallic
frameworks. Europhys Lett 2005;72(4):569e75.
[51] Lee YS, Ouyang CY, Suh JY, Fleury E, Cho YW, Shim JH. Role
of alloying elements in vanadium-based binary alloy
membranes for hydrogen separation. J Membr Sci
2012;423:332e41.
[52] Kong XS, Wu XB, Liu CS, Fang QF, Hu QM, Chen JL, Luo GN. First-
principles calculations of transition metal solute interactions
with hydrogen in tungsten. Nucl Fusion 2016;56(2):14.
[53] Shen HH, Hu JT, Li PC, Huang G, Zhang JW, Zhang JC,
Mao YW, Xiao HY, Zhou XS, Zu XT, Long XG, Peng SM.
Compositional dependence of hydrogenation performance of
Ti-Zr-Hf-Mo-Nb high-entropy alloys for hydrogen/tritium
storage. J Mater Sci Technol 2020;55:116e25.
[54] Lochan RC, Head-Gordon M. Computational studies of
molecular hydrogen binding affinities: the role of dispersion
forces, electrostatics, and orbital interactions. Phys Chem
Chem Phys 2006;8(12):1357e70.
[55] El Khatabi M, Bhihi M, Naji S, Labrim H, Benyoussef A, El
Kenz A, Loulidi M. Study of doping effects with 3d and 4d-
transition metals on the hydrogen storage properties of
MgH2. Int J Hydrogen Energy 2016;41(8):4712e8.
[56] Guo S, Liu CT. Phase stability in high entropy alloys:
formation of solid-solution phase or amorphous phase. Prog
Nat Sci 2011;21(6):433e46.