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 7 ( 2 0 2 2 ) 2 2 8 9 3 e2 2 9 0 0

Available online at www.sciencedirect.com

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

Notable hydrogen storage in TieZreVeCreNi high

entropy alloy

Abhishek Kumar a, Thakur Prasad Yadav a,*,

Nilay Krishna Mukhopadhyay b
a
Hydrogen Energy Centre, Department of Physics, Institute of Science, Banaras Hindu University, Varanasi-221005,
Uttar Pradesh, India
b
Department of Metallurgical Engineering, Indian Institute of Technology (Banaras Hindu University), Varanasi-
221005, India

highlights

Synthesis of pure C14 type hexagonal Laves phase high-entropy alloy in TieZreVeCreNi equiatomic system.

The developed new materials with 1.52 wt% hydrogen storage capacities.

A stable cyclic stability in reversible hydrogen storage capacity of TieZreVeCreNi equiatomic alloy.

article info abstract

Article history: In the present investigation, we discussed the synthesis, structural and hydrogen storage
Received 8 January 2022 behavior of high-entropy TieZreVeCreNi equiatomic intermetallic alloy. This alloy was
Received in revised form synthesized by arc melting in an argon atmosphere where base pressure was in the order
28 April 2022 of 105 atm before purging with argon gas. The X-ray diffraction study revealed that the
Accepted 12 May 2022 alloy is C14 type hexagonal Laves phase. The pressure composition isotherms (PCI) of this
Available online 4 June 2022 alloy were investigated with pressure ranges at 0e40 atmosphere. The total hydrogen
storage capacities were found to be 1.52 wt%. The reversible hydrogen storage capacity was
Keywords: quite stable and only slight decreases in the storage capacity was observed after 10 cycles
Multicomponent intermetallic during hydrogen soaking. The demonstrations of hydrogen storage capacity of the TieZreV
alloys eCreNi equiatomic alloy were thus established, indicating the future potential of devel-
High-entropy alloy oping this class of high entropy intermetallic based materials for hydrogen storage.
Hydrogen energy © 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Hydrogen storage

detrimental consequences due to pollution. One of the most

Introduction
Due to the scarcity of the fossil resources, the globe is expe-
riencing an energy crisis. It requires immediate attention for
meeting the energy demand with more efficient and clean
alternative energy sources that can protect the globe from
essential alternative energy sources is considered to be
hydrogen, which is a 100% pure fuel that can be used in cars,
buildings, portable power, and a variety of other applications.
The hydrogen economy encompasses hydrogen generation,
storage, and distribution/application, among other things; of

* Corresponding author.
E-mail address: thakurp.yadav@bhu.ac.in (T.P. Yadav).
https://doi.org/10.1016/j.ijhydene.2022.05.107
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
22894 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 7 ( 2 0 2 2 ) 2 2 8 9 3 e2 2 9 0 0
these, storage is now the most significant. A multicomponent
High Entropy Alloy (HEA) is an emerging class of advanced
materials leading to a new field in materials science due to
their superior mechanical, physical and functional properties,
unlike that of conventional alloys which are based on one or
two principal elements [1,2]. The term HEAs was firstly coined
by Yeh et al. [3] in 2004 and the concept of a multicomponent
system was demonstrated by Yeh et al. and Cantor et al. [4]. It
contains five or more than five elements, each with a con-
centration between 5 and 35 atomic percent. HEAs exhibit
high chemical disorder, which can stabilize the single solid
solution phases with simple crystal structures like body-
centered cubic (BCC), face-centered cubic (FCC), and hexago-
nal close-packed (HCP) in the multi-component systems [5].
The hydrogen storage property of HEAs has been of much
interest. Solid-state storage is a viable, efficient, and cost-
effective way [6,7] for hydrogen storage, where hydrogen is
stored in a material either in the form of atoms or in the form
of H2 molecules. Hence, designing of new type of hydrogen
storage materials with specific microstructure is very
rewarding in which the number of interstices would be
available for hydrogen atoms [8,9]. Some intermetallic phases
like Laves phase-based alloys open a new area of research as
hydrogen storage materials [10].
The first investigation into HEAs for application-based
hydrogen storage property was investigated by Kao et al. in
2010 [10]. He investigated hydrogen storage capacity range
Fig. 1 e Schematic diagram of the synthesis protocol for Ti20Zr20V20Cr20Ni20 high entropy alloy.
between 0.03 and 1.8 wt % for CoFeMnTixVyZrz where, x, y, and
z that can vary from the range 0.5 < x > 2.5; 0.4 < y > 3.0; and 0.4
< z > 3.0. X-ray diffraction revealed that these compositions
are not the single-phase solid solutions but they contain also
an intermetallic phase, i.e. hexagonal C14-type Laves phases
(P63/mmc). Kunce et al. [6] reported the 2.3 wt% hydrogen
storage capacity after additional annealing and showed 1.8 wt
% hydrogen storage capacities in TiZrNbMoV, synthesized by
Laser Engineered Net Shaping (LENS) technique. This HEA
system represents a two-phase system with a BCC type phase
as a major one and the orthorhombic NbTi4 intermetallic
phase as a minor one. Kunce et al. also reported ZrTiVCrFeNi
as C14 Laves phase with 1.81 wt% hydrogen storage capacity
[11]. Sahlberg et al. [12] reported 2.7 wt% hydrogen storage
capacities in BCC TiVZrNbHf HEA synthesized by arc melting.
This is the first such report which proposed high hydrogen
capacity performance compared to the other HEAs and con-
ventional alloys. Zhang et al. [13] reported the TiZrNbTa HEAs
with a BCC phase and showed that after activation at high
temperature, the maximum hydrogen storage capacities at
room temperature to be 1.40 wt%. Zepon et al. [14] revealed the
formation of BCC phase in complex concentrated alloy by high
energy ball milling (HEBM) for hydrogen storage material.
They demonstrated that MgZrTiFe0.5Ni0.5 which was synthe-
sized in argon atmosphere by HEBM absorbed hydrogen as
1.2 wt%. The hydrogenation was accompanied by an incom-
plete transformation from BCC to FCC. Montero et al. [15]
 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 7 ( 2 0 2 2 ) 2 2 8 9 3 e2 2 9 0 0 22895

investigated the single BCC phase in Ti0.325V0.275Zr0.125Nb0.275
multi-principal multicomponent HEAs synthesized by HEBM
with 2.5 wt% superior hydrogen storage capacity. In recent
study, Dewangan et al. [16] investigated hydrogen sorption
through volumetric method on AlCrFeMnNiW, and at room
temperature the maximum storage capacity was estimated to
be 0.616 wt%. Marco et al. [17] synthesized the MgTiVCrFe
HEAs by mechanical alloying via HEBM under hydrogen at-
mosphere and maximum sorption capacity was found to be
0.9 wt%. MgVAlCrNi HEA reported by Strozi et al. [18] as a
single phase BCC lightweight HEAs with 0.3 wt% of hydrogen
storage capacity which is low because most of the alloying
elements of this system are positive, only V has negative
enthalpy of hydrogen solution. Strozi et al. [18] investigated
for the first time the importance of enthalpy of hydrogen so-
lution for designing light weight HEAs for hydrogen storage
application. Shen et al. [19] reported compositional dependent
hydrogen storage performance in TieZreHfeMoeNb HEA. In
the same way, the high entropy MgAlTiFeNi HEA was pro-
duced by reactive milling with 0.94 wt% hydrogen storage
capacity by Cardoso et al. [20]. Floriano et al. [21] studied A3B2
type TiZrNbCrFe HEA to represent C14 type major Laves phase
with BCC minor phase, which desorbs 1.9 wt% hydrogen at
473 K. Some cycles of hydrogenation fully converted C14 and
BCC phase into C14 and FCC hydride phases [22,23]. Recently
Montero et al. [24] observed 2.7 wt% hydrogen absorption
within 1 min at room temperature for Mg0.10Ti0.30V0.25Zr0.10-
Nb0.25 HEA containing a major BCC phase.
The present studies aim at selecting the hydride-forming
elements (Ti, Zr, V) along with non-hydride forming ele-
ments (Cr, Ni) and investigated the hydrogen storage proper-
ties of TieZreVeCreNi intermetallic HEA [25], which was
synthesized by arc melting technique in the presence of Ar
atmosphere and structurally characterized by X-ray diffrac-
tion (XRD) followed by Jana 2006 Rietveld Refinement. The
pressure composition temperature isotherms involving for
hydrogen storage investigation were explored.
Table 1 e Lattice Parameters and refinement parameters
obtained from powder x-ray diffraction data of as-cast
sample.
Refine Parameter and phase data
Unit-Cell Parameters a ¼ b ¼ 5.0875  A, c ¼ 8.2884,
a ¼ b ¼ 90 , g ¼ 120
Space Group P63/mmc (Space Group ¼ 194)
R- Factor Rp ¼ 4.68%, wRp ¼ 6.37%,
GOF ¼ 1.18%,
Volume V ¼ 185.80 A3

Fig. 2 e (a) XRD pattern of TieZreVeCreNi alloy system, (b) Rietveld refinement of the bulk alloys, (c) XRD pattern after first
cycle dehydrogenation and (d) XRD pattern after 10 cycle dehydrogenation.
22896 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 7 ( 2 0 2 2 ) 2 2 8 9 3 e2 2 9 0 0

Experimental details
The high purity materials for the synthesis of the
TieZreVeCreNi system was procured from Alfa Aeser with
the purity of materials Ti (99.99%), Zr (99.90%), V (99.99%), Cr
(99.96%) and Ni (99.99%). The calculated enthalpy of mixing
(DHmix) was found to be 21.76 kJ/mol for this HEA system;
therefore this alloy composition may be suitable for the syn-
thesis of a single phase HEA. Using a cylindrical steel mould
equipped with a hydraulic press at an operating pressure of
3  105 N/m2, all the constituent materials with equiatomic
ratio were taken for consolidating as a palette. The palette
(about 10 g by weight) was then used for melting and casting
by utilizing an arc melting technique in an argon atmosphere.
It was re-melted five times for complete homogeneity. The
detailed synthesis processes have been demonstrated using
schematic diagram as shown in Fig. 1. The characterization
was performed using an X'Pert PRO PANalytical XRD diffrac-
tometer with a graphite monochromator and Nickel-filtered
Cu radiation (¼ 1.5402 A, CuKa working at 45 kV and 40 mA)
in Bragg-Brentano mode. All of the measurements were taken

in the 2q range: 10e80 in a continuous scan mode with the

step size of 0.02 and scan step length of 1.5 s. The structural
refinement of the as-synthesized HEA was carried out using
Rietveld's entire profile fitting approach, which is based on
JANA2006 and uniquely developed to tune structural param-
eters simultaneously using a least square method and Le-Bail
fitting. Each run of the hydrogen sorption measurement used
500 mg of the sample through an Advanced Material
Corporation-supplied pressure composition isotherm (PCI)
equipment (Pittsburgh, USA). The hydrogen desorption ca-
pacity and kinetics were measured using temperature pro-
grammed desorption (TPD) at 5 C/min heating rate. The
hydrogen storage capacity and absorption kinetics were
investigated in soaking mode under 100 atm hydrogen
pressures.
Results and discussion
Structure characterization was carried out using XRD tech-
niques to determine the crystal structure of the as-cast
TieZreVeCreNi HEAs, as illustrated in Fig. 2. All the

Fig. 3 e (a) Hydrogenation curve of bulk as-cast Ti20Zr20V20Cr20Ni20 HEA, (b) TPD curves of hydrogenated kinetics curve of
bulk as-cast Ti20Zr20V20Cr20Ni20 HEA, (c) pressure composition isotherm curve for absorption and desorption of bulk as-cast
Ti20Zr20V20Cr20Ni20 HEA and (d) Number of Cycles vs. hydrogen storage capacity of bulk as-cast Ti20Zr20V20Cr20Ni20
HEAupto10 cycles.
 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 7 ( 2 0 2 2 ) 2 2 8 9 3 e2 2 9 0 0 22897

diffraction peaks (shown in Fig. 2a) matched with the hexag-
onal C14 laves phase (MgZn2 type, P63/mmc space group). The
XRD Le-Bail fitting plot has been shown in Fig. 2(b). The
goodness-of-fit (GOF) of this refinement is 1.18. The refine-
ment data validate the TieZreVeCreNi HEA system with unit
cell parameters of a ¼ b ¼ 5.0875 A, c ¼ 8.2884 
A for C14 Laves
phase.
The calculated XRD pattern has been shown by dotted line
after refining all the data including lattice parameters, profile
shape and background, giving rise to close match with the
experimental data. The peak shape was assumed to be a
pseudo-Voigt (pV) function with asymmetry. The background
of each pattern was fitted by a Legendre polynomial function
of degree and the least squares refinement technique was
adopted for minimizing the difference between experimental
and calculated diffraction pattern by using the residual
function,
X  2
Ry ¼ wi yðobsÞi  yðcalcÞi
i
to be 1.52 wt% of H2 after 300 min under similar conditions of
temperature and pressure. This is the first demonstration of the
hydrogen storage behaviour of the as-cast TieZreVeCreNi
HEA with absorption kinetics. The hydrogen desorption ca-
pacity and kinetics were measured using TPD with 5  C/min
heating rate up to 300  C and has been shown in Fig. 3(b). The
desorption up to ~200  C temperature was quite slow, however
at temperature above 200  C, the desorption kinetic was very
fast and the total desorption has been finished by 300  C tem-
perature. The maximum desorption capacity was observed
~1.51 wt%, therefore there is very less probability of the for-
mation of stable hydride in this alloy system. The representa-
tive PCI for absorption and desorption of the bulk as-cast
TieZreVeCreNi HEA has been shown in Fig. 3(c). The regions
observed were found to be nearly flat with equilibrium pres-
sures below 5 atm for PCI-absorption at room temperature
(~32  C) and PCI-desorption at 200  C. The PCI-absorption and
PCI-desorption was measured up to 40 atm pressure and the
(1) maximum hydrogen storage capacity was found to be 1.53 wt%.

X  
 
yci ¼ s LðhklÞ F2ðhklÞ 4i ð2qi  2qhkl ÞPðhklÞ A þ ybi (2)
j

where y(obs)i ¼ observed intensity and y(calc)i ¼ calculated

intensity.
Where, s ¼ scaling factor, L(hkl) ¼ Lorentz Polarization and
multiplicity Factors, P(hkl) ¼ Preferred Orientation Function, A
¼ Absorption Factor, F(hkl) ¼ structure factor, ybi ¼ background
intensity. After importing the data different refining parame-
ters (i.e. unit cell, background, peak profile etc.) were set in
order to achieve the best Le-Bail fit. By checking all the refining
parameters one by one, the refinement of XRD profile was
initiated and the positions of the peaks were corrected by
successive refinements at different cycles. The experimental
profile was fitted with the most suitable pseudo-Voigt func-
tion because it includes both the particle size and strain
broadening of the experimental profiles and represented by,

pVi;k ¼ hLi;k þ ð1  hÞGi;k (3)

where L and G are the Lorentzian and Gaussian components

respectfully. After getting this best profile fit, for the structural
analysis, the atomic coordinates are entered in the program
and by refining all the data, the program gives the final
structure and detailed calculated parameters are given in
Table 1. The XRD pattern of dehydrogenated after one cycle
and ten cycle of the TieZreVeCreNi HEA samples have been
shown Fig. 2(c) and (d) respectively which revealed that there
was no indication of the formation of any new phases. The
XRD results confirmed that the stability of C14 Laves phase in
the present alloy composition remained unchanged before
and after de/re-hydrogenation.
The hydrogen sorption properties of the as-cast
TieZreVeCreNi HEA were investigated and the results are
shown in Fig. 3. The hydrogenation of bulk TieZreVeCreNi
HEA has been checked after five time of activation at room
temperature (32 C) and 100 atm of H2 pressure. The results are Fig. 4 e Scanning electron micrograph of the (a) bulk as-
displayed in Fig. 3(a). As it can be seen from Fig. 3(a) that the as- cast Ti20Zr20V20Cr20Ni20 HEA (b) dehydrogenated alloy after
cast TieZreVeCreNi HEA could absorb ~1.2 wt% of H2, in 10 cycle exhibiting intra grain cracking due to lattice
50 min and the maximum storage absorbed capacity was found expansion upon hydrogenation.
22898 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 7 ( 2 0 2 2 ) 2 2 8 9 3 e2 2 9 0 0
Table 2 e Reported hydrogen storage capacity in Laves phase.
S.No HEAs Composition Synthesis Method
1. CoFeMnTixVyZrz Arc melting
2. ZrTiVCrFeNi LENS
3. Ti0.30V0.25Zr0.10Nb0.25Ta0.10 Arc melting
4. TiZrNbCrFe Arc melting
5. Ti20Zr20V20Cr20Ni20 Arc melting
The hydrogen absorption and desorption curve (Fig. 3(c)) shows
the plateau pressure of bulk as-cast TieZreVeCreNi HEA,
which is below 5 atm and remains nearly invariant.
It is known that there is a direct relationship between
plateau pressure and application of hydrogen storage mode,
therefore this low plateau pressure TieZreVeCreNi HEA will
be a suitable material for practical application. Since revers-
ibility/cycling are another important characteristic of any
viable hydride, we checked the reversibility of the sample by
performing cyclic hydrogenation and de-hydrogenation ex-
periments. The hydrogenation storage capacity up-to 10 cycles
was performed to check the cyclic stability of TieZreVeCreNi
HEA. Fig. 3(d) shows the hydrogen storage capacity of
TieZreVeCreNi HEA during 10 cycles of absorption and
desorption. It can be seen that even after 10 cycles,
TieZreVeCreNi HEA shows good cyclic stability and the ca-
pacity though it degrades slightly from ~1.52 wt % to ~1.49 wt%
of H2. Scanning electron microscopy (SEM) of the powder par-
ticle surface was used to investigate the surface morphology of
dehydrogenated alloys. Secondary electron micrographs of as
cast Ti20Zr20V20Cr20Ni20 HEA and dehydrogenated Ti20Zr20V20-
Cr20Ni20 HEA alloys are shown in Fig. 4(a) and (b), respectively.
After 10 cycles of hydrogenation/dehydrogenation several
crackings are clearly visible on the surface microstructure.
However, the samples do not break down into small particles;
instead, fissures appear in the grains.
It is interesting to note that the present HEA is associated
with five elements in which Ti, V, Zr elements have negative
enthalpy of hydrogen solution [26]. The experimental
enthalpy of formation (in kJ/mol H2) is 136,-70, 164 for Ti,
V, Zr, elements with hydrogen respectively. All these data
were selected from extending Miedema's model to predict
hydrogen content in metal hydrides [26]. Cr and Ni also have
negative enthalpy of hydrogen solution but it is very much
less i.e. 12 and 9 (kJ/mol H2) respectively [26]. Therefore, Cr
and Ni formed the hydride only under high pressure and high
temperature. Moreover, Cr and Ni were used as a catalyst for
enhancing the performance of hydrogen absorption and
desorption in metal hydride [27,28] where Ni and Cr in the
alloy system helps destabilise the hydrogen molecule, and
form the hydrogen atom. It also plays an essential role in
improving the desorption kinetics for the alloy system.
Therefore, the present HEA i.e. TieZreVeCreNi system with
hydride forming elements (Ti, V, Zr) and weak hydride
forming elements (Ni, Cr) are an interesting combination as
notable hydrogen storage materials. The calculated enthalpy
of mixing (DH mix) for the TieZreVeCreNi HEA system is
21.76 kJ/mol. It should be noted that as this alloy is not
strictly AB2 type Laves phase, therefore many vacancies in B-
Phase Storage Capacity in wt% Reference
C14 Laves Phase 0.03e1.80 wt% Kao et al., 2010 [10]
C14 Laves Phase 1.81 wt% Kunce et al., 2013 [11]
BCC 2.2 wt% Montero et al., 2020 [29]
C14 Laves Phase(Major) 1.9 wt% Floriano et al., 2021 [21]
BCC(Minor)
C14 Laves Phase 1.52 wt% Present Investigation
sites are expected, which may favour hydrogen absorption
because the structure is open and relaxed. It is logical that an
AB2 alloy with a precise composition will not attract and
absorb so much hydrogen, though all of which will occupy
the interstitial sites of the Laves phase structure. Large
atoms like Ti and Zr are represented by A, while smaller
atoms are represented by B (V, Cr, Ni). Thus the current alloy
is of the type AB1.5, with a combination of strong and weak
hydride forming elements. However, the maximum reported
hydrogen storage capacity in BCC HEA is reported to be
3.51 wt% [29,30]. In the case of Laves phase, the maximum
reported hydrogen storage capacity was about 1.91 wt% as
shown in Table 2. The advantage of selecting the Laves phase
HEA instead of the BCC HEA is that the Laves phase has po-
tential for better absorption and desorption kinetics than
that of the BCC HEAs [31]. Some comparative results of BCC
and C14 Laves phase-based HEAs are provided in Table 2 for
better understanding.
Conclusions
We presented a facile and effective route for the synthesis of
equatomic Ti20Zr20V20Cr20Ni20 intermetallic HEAs by arc
melting in an argon atmosphere. The as-cast alloy has shown
the evolution of a single phase hexagonal C14 Laves phase-
structure with the lattice parameters, a ¼ 5.08  A and
c ¼ 8.41 A.This high entropy intermetallic alloy exhibited
higher desorption capacity of ~1.52 wt% and also was acti-
vated easily. This intermetallic based alloy with equiatomic
composition led to low plateau pressure (below five atmo-
sphere) hydrogen storage materials. Thus the present study
suggests the scope for the further investigation on the hy-
drogenation behaviour of TieZreVeCreNi based intermetallic
HEAs with light weight hydrides for developing new class of
hydrogen storage materials.
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.
Acknowledgements
The authors would like to thank Prof. M.A. Shaz and Dr. S.S.
Mishra for many useful discussions on high-entropy alloys.
 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 7 ( 2 0 2 2 ) 2 2 8 9 3 e2 2 9 0 0
The financial support from the Department of Science and
Technology (No. DST/TMD/HFC/2K18/70(c)) is thankfully
acknowledged. One of the authors (A. K.)would like to
acknowledge the Council of Scientific & Industrial Research-
New Delhi, India for Junior Research Fellowship (No. 09/
013(0952)/2020-EMR-I).
references
[1] Miracle DB, Senkov ON. A critical review of high entropy
alloys and related concepts. Acta Materialia
2017;122:448e511. https://doi.org/10.1016/
j.actamat.2016.08.081.
[2] Senkov ON, Miracle DB, Chaput KJ, Couzinie J-P.
Development and exploration of refractory high entropy
alloysda review. Journal of Materials Research
2018;33:3092e128. https://doi.org/10.1557/jmr.2018.153.
[3] Yeh J-W, Chen S-K, Lin S-J, Gan J-Y, Chin T-S, Shun T-T, et al.
Nanostructured high-entropy alloys with multiple principal
elements: novel alloy design concepts and outcomes.
Advanced Engineering Materials 2004;6:299e303. https://
doi.org/10.1002/adem.200300567.
[4] Cantor B, Chang ITH, Knight P, Vincent AJB. Microstructural
development in equiatomic multicomponent alloys.
Materials Science and Engineering: A 2004;375e377:213e8.
https://doi.org/10.1016/j.msea.2003.10.257.
[5] Chen P, Zhu M. Recent progress in hydrogen storage.
Materials Today 2008;11:36e43. https://doi.org/10.1016/
S1369-7021(08)70251-7.
[6] Kunce I, Polanski M, Bystrzycki J. Microstructure and
hydrogen storage properties of a TiZrNbMoV high entropy
alloy synthesized using Laser Engineered Net Shaping
(LENS). International Journal of Hydrogen Energy
2014;39:9904e10. https://doi.org/10.1016/
j.ijhydene.2014.02.067.
[7] Youssef KM, Zaddach AJ, Niu C, Irving DL, Koch CC. A novel
low-density, high-hardness, high-entropy alloy with close-
packed single-phase nanocrystalline structures. Materials
Research Letters 2015;3:95e9. https://doi.org/10.1080/
21663831.2014.985855.
[8] Yadav TP, Shahi RR, Srivastava ON. Synthesis,
characterization and hydrogen storage behaviour of AB2
(ZrFe2, Zr(Fe0.75V0.25)2, Zr(Fe0.5V0.5)2 type materials.
International Journal of Hydrogen Energy 2012;37:3689e96.
https://doi.org/10.1016/j.ijhydene.2011.04.210.
[9] Zhang F, Zhao P, Niu M, Maddy J. The survey of key
technologies in hydrogen energy storage. International
Journal of Hydrogen Energy 2016;41:14535e52. https://
doi.org/10.1016/j.ijhydene.2016.05.293.
[10] Kao Y-F, Chen S-K, Sheu J-H, Lin J-T, Lin W-E, Yeh J-W, et al.
Hydrogen storage properties of multi-principal-component
CoFeMnTixVyZrz alloys. International Journal of Hydrogen
Energy 2010;35:9046e59. https://doi.org/10.1016/
j.ijhydene.2010.06.012.
[11] Kunce I, Polanski M, Bystrzycki J. Structure and hydrogen
storage properties of a high entropy ZrTiVCrFeNi alloy
synthesized using Laser Engineered Net Shaping (LENS).
International Journal of Hydrogen Energy 2013;38:12180e9.
https://doi.org/10.1016/j.ijhydene.2013.05.071.
[12] Sahlberg M, Karlsson D, Zlotea C, Jansson U. Superior
hydrogen storage in high entropy alloys. Scientific Reports
2016;6:36770. https://doi.org/10.1038/srep36770.
[13] Zhang C, Wu Y, You L, Cao X, Lu Z, Song X. Investigation on
the activation mechanism of hydrogen absorption in
TiZrNbTa high entropy alloy. Journal of Alloys and
22899
Compounds 2019;781:613e20. https://doi.org/10.1016/
j.jallcom.2018.12.120.
[14] Zepon G, Leiva DR, Strozi RB, Bedoch A, Figueroa SJA,
Ishikawa TT, et al. Hydrogen-induced phase transition of
MgZrTiFe0.5Co0.5Ni0.5 high entropy alloy. International
Journal of Hydrogen Energy 2018;43:1702e8. https://doi.org/
10.1016/j.ijhydene.2017.11.106.
[15] Montero J, Zlotea C, Ek G, Crivello J-C, Laversenne L,
Sahlberg M. TiVZrNb multi-principal-element alloy:
synthesis optimization, structural, and hydrogen sorption
properties. Molecules 2019;24. https://doi.org/10.3390/
molecules24152799.
[16] Dewangan SK, Sharma VK, Sahu P, Kumar V. Synthesis and
characterization of hydrogenated novel AlCrFeMnNiW high
entropy alloy. International Journal of Hydrogen Energy
2020;45:16984e91. https://doi.org/10.1016/
j.ijhydene.2019.08.113.
[17] de Marco MO, Li Y, Li H-W, Edalati K, Floriano R. Mechanical
synthesis and hydrogen storage characterization of MgVCr
and MgVTiCrFe high-entropy alloy. Advanced Engineering
Materials 2020;22:1901079. https://doi.org/10.1002/
adem.201901079.
[18] Strozi RB, Leiva DR, Huot J, Botta WJ, Zepon G. Synthesis and
hydrogen storage behavior of MgeVeAleCreNi high entropy
alloys. International Journal of Hydrogen Energy
2021;46:2351e61. https://doi.org/10.1016/
j.ijhydene.2020.10.106.
[19] Shen H, Hu J, Li P, Huang G, Zhang J, Zhang J, et al.
Compositional dependence of hydrogenation performance of
Ti-Zr-Hf-Mo-Nb high-entropy alloys for hydrogen/tritium
storage. Journal of Materials Science & Technology
2020;55:116e25. https://doi.org/10.1016/j.jmst.2019.08.060.
[20] Cardoso KR, Roche V, Jorge Jr AM, Antiqueira FJ, Zepon G,
Champion Y. Hydrogen storage in MgAlTiFeNi high entropy
alloy. Journal of Alloys and Compounds 2021;858:158357.
https://doi.org/10.1016/j.jallcom.2020.158357.
[21] Floriano R, Zepon G, Edalati K, Fontana GLBG, Mohammadi A,
Ma Z, et al. Hydrogen storage properties of new A3B2-type
TiZrNbCrFe high-entropy alloy. International Journal of
Hydrogen Energy 2021;46:23757e66. https://doi.org/10.1016/
j.ijhydene.2021.04.181.
[22] Shahi RR, Gupta AK, Kumari P. Perspectives of high entropy
alloys as hydrogen storage materials. International Journal of
Hydrogen Energy 2022. https://doi.org/10.1016/
j.ijhydene.2022.02.113.
[23] Yadav TP, Kumar A, Verma SK, Mukhopadhyay NK. High-
entropy alloys for solid hydrogen storage: potentials and
prospects. Transactions of the Indian National Academy of
Engineering 2022;7:147e56. https://doi.org/10.1007/s41403-
021-00316-w.
[24] Montero J, Ek G, Sahlberg M, Zlotea C. Improving the
hydrogen cycling properties by Mg addition in Ti-V-Zr-Nb
refractory high entropy alloy. Scripta Materialia
2021;194:113699. https://doi.org/10.1016/
j.scriptamat.2020.113699.
[25] Yadav TP, Mukhopadhyay S, Mishra SS, Mukhopadhyay NK,
Srivastava ON. Synthesis of a single phase of high-entropy
Laves intermetallics in the TieZreVeCreNi equiatomic alloy.
Philosophical Magazine Letters 2017;97:494e503. https://
doi.org/10.1080/09500839.2017.1418539.
[26] Herbst JF. On extending Miedema's model to predict
hydrogen content in binary and ternary hydrides. Journal of
Alloys and Compounds 2002;337:99e107. https://doi.org/
10.1016/S0925-8388(01)01939-9.
[27] Yang X, Hou Q, Yu L, Zhang J. Improvement of the hydrogen
storage characteristics of MgH2with a flake Ni nano-catalyst
composite. Dalton Transactions 2021;50:1797e807. https://
doi.org/10.1039/d0dt03627g.
22900 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 7 ( 2 0 2 2 ) 2 2 8 9 3 e2 2 9 0 0

[28] Vyas D, Jain P, Agarwal G, Jain A, Jain IP. Hydrogen storage
properties of Mg2Ni affected by Cr catalyst. International
Journal of Hydrogen Energy 2012;37:16013e7. https://doi.org/
10.1016/j.ijhydene.2012.08.039.
[29] Montero J, Ek G, Laversenne L, Nassif V, Zepon G. Hydrogen
storage properties of the refractory TieVeZreNbeTa multi-
principal element alloy. J Alloys Compd 2020;835:155376.
https://doi.org/10.1016/j.jallcom.2020.155376. Elsevier.
[30] Marques F, Balcerzak M, Winkelmann F, Zepon G,
Felderhoff M. Review and outlook on high-entropy alloys for
hydrogen storage. Energy Environ Sci 2021;14:5191. https://
doi.org/10.1039/d1ee01543e.
[31] Murty BS, Yeh J-W, Ranganathan S, Bhattacharjee PP. High-
Entropy Alloys. Netherlands: Elsevier Science; 2019.