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 ) 1 1 8 2 4 e1 1 8 3 1

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Short Communication

Effects of different substitution concentration and

configuration on some properties of magnesium
hydrides substituted with titanium; Ab initio study

Myong-Bom Pang a, Song-Il Hong b, Su-Il Ri b,*, Jong-Chol Kim b

a
Department of Solid Material, University of Sciences. Unjong District, Pyongyang, Democratic People’s Republic of
Korea
b
Department of Computational Material, Institute of Physics. Unjong District, Pyongyang, Democratic People’s
Republic of Korea

highlights

Overall bonding strength is weakened by titanium substitution.

Mg4Ti2H6 has too low desorption temperature for dehydrogenation.

Proper substitution configuration is necessary for good property.

Mg14Ti4H36 is a good candidate as hydrogen storage material.

Single substitution has advantages compared with co-substitution.

article info abstract

Article history: We investigated hydrogen some properties of magnesium hydrides substituted with tita-
Received 15 October 2020 nium by a first principles calculation. In order to evaluate effect of different substitution
Received in revised form concentration and configuration on desorption temperature and bulk modulus, we con-
30 December 2020 structed five systems such as Mg4Ti2H12, Mg8Ti2H20, Mg16Ti2H36, Mg14Ti4H36 and Mg12Ti6H36
Accepted 7 January 2021 by using 1  1  3, 1  1  5 and 3  3  1 super cell of pure magnesium hydride. Among the
Available online 5 February 2021 investigated systems, Mg14Ti4H36 system showed the best performance as hydrogen stor-
age material in the complex viewpoints of substitution energy, desorption temperature and
Keywords: bulk modulus. In addition to, our results demonstrated that not only substitution con-
Magnesium hydride centration but also configuration plays vital effect on material’s property of magnesium
Substitution concentration hydrides. Bader charge analysis explained the reason why desorption temperature is fallen
Desorption temperature down by substitution with titanium.
Bulk modulus © 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: su-i.ri@star-co.net.kp (S.-I. Ri).
https://doi.org/10.1016/j.ijhydene.2021.01.048
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 ) 1 1 8 2 4 e1 1 8 3 1
Introduction
Hydrogen is convenient and renewable energy source, but
hydrogen storage is challenge in the face of practical appli-
cations. In general, preparing metal hydrides is one of po-
tential methods for high hydrogen storage density [1e5]. Pure
magnesium hydride has not been yet employed as hydrogen
storage material (HSM) due to high desorption temperature,
although it is a cheap and good candidate for high density of
hydrogen storage [6]. In order to utilize magnesium hydride in
practical situations, a proper catalyst are required necessarily,
while it must fallen down desorption temperature to the range
of 60e120C.
In last decades, many investigations have been per-
formed for improving dehydrogenation property of magne-
sium hydride [7e10]. Researchers showed that magnesium
hydride was destabilized by alloying with other metals and
thus had reduced desorption temperature. MgH2eTm
(Tm ¼ transition metals) composites prepared by mechani-
cal milling showed more advantage hydrogen ad/desorption
properties than the milled pristine MgH2 [11e13]. MgH2eV
composite exhibited rapid desorption kinetics at low tem-
perature and MgH2eTi composite exhibited rapid absorption
property. Mechanical milling with transition metals didn’t
changed formation enthalpies, but activation energies were
reduced considerably.
MgH2/TiH2 mixture has been prepared from MgH2 and TiH2
by a high-energy, high-pressure milling technique [14]. This
composite decomposed into metal phase Mg and hydride
phase TiH2 at 126  Ce313  C with releasing a large amounts of
hydrogen (5.91 wt%). This result is a good example that shows
a catalytic effect of titanium, while theoretical result sup-
ported also that the ad/desorption property of MgH2 could be
improved by titanium [15].
Alloying is an effective method for improving performance
of metal based hydrogen storage materials. In order to simu-
late alloying effect, many researchers employed the rutile type
structure of MgH2 and substituted some magnesium atoms
with transition metals. Alloying effect with other elements
such as transition metals play significant role in enhancing
ad/desorption performance of magnesium hydride, too [6,16].
Theoretical investigation demonstrated that doping with
alloying elements such as Al, Ti, Fe and Ni induced destabili-
zation in magnesium hydride and thus heats of formation and
desorption temperatures were decreased by doping effects
[17]. In order to simulate mechanical milling and alloying ef-
fect, various magnesium hydrides substituted with transition
metals were investigated by a first principle calculations
[18e22]. The authors selected a certain substitution site and
investigated how some properties such as chemical bonding,
cohesive energy and desorption temperature were changed by
substitutions, while they didn’t considered effect of different
substitution concentration. In the reference [23,24], the au-
thors investigated Mg/MgH2eTiH2 composite hydride and
MgH2/TiH2 interface by using their theoretical models for
simulating composite hydride. The enthalpy change for the
Mg/MgH2eTiH2 system was about 7 kJ/mol H2 lower than that
for ball-milled MgH2. The experimental result was reported
that TiH2 templated over graphene has a significant effect on
11825
the hydrogen sorption characteristics of MgH2/Mg [25]. In the
system, the onset desorption temperature was about 204 C.
Titanium has not only hcp structure under ambient con-
dition as magnesium, but also is alloyed with magnesium. The
experimental result was reported that small energy is
required in order to replace Mg atom of MgH2 with titanium. In
addition to, the experimental fact was also reported that the
high hydrogenation performance of MgeFeeTi thin films is
due to its improved adsorption kinetics [26,27].
It is necessary to simulate magnesium based hydrides with
different titanium concentration. To the best our knowledge,
the systematic investigation has not been yet reported in lit-
eratures. In this paper, we researched magnesium based hy-
drides with different titanium concentration and
configuration by a first principle calculation. We utilized the
rutile type structure in order to simulate the alloy hydrides
based on magnesium.
Computational method
The initial lattice parameters of a unit cell of pure MgH2 were
set to be a ¼ b ¼ 4.535  A and c ¼ 3.033  A, respectively [17]. In
order to describe various substitution configurations, we
employed 1  1  3, 1  1  5 and 3  3  1 super cell as unit
cells, and magnesium atoms in Wyckoff position 2a were
substituted with titanium atoms. In case of 3  3  1 super cell,
4 g or both 2a and 4 g substituted systems were researched
additionally for more detail investigation. The magnesium
based hydrides substituted with titanium were denoted to
Mg4Ti2H12, Mg8Ti2H20, Mg16Ti2H36, Mg14Ti4H36 and Mg12Ti6H36,
respectively.
We carried out various computations by using QUANTUM-
ESPRESSO program package within the density functional
theory (DFT) [28]. Perdew-Wang 91 (PW91) was employed as
the exchange-correlation energy functional [29] and kinetic
energy cutting was set to be 55 Ry in expanding wave func-
tions by plane wave. First of all, we performed relaxation
calculations for obtaining optimized structures and then
performed self-consistent calculations. The total energy cri-
terion in all the calculations was set to be 106 Ry, and initial
structures were fully relaxed by BFGS (Broyden-Fletcher-
Goldfarb-Shanno) method [30] until Hellman-Feynman forces
were less than 4  105
Ry/bohr. For accurate calculation, we also used 9  9  3 for
1  1  3 super cell, 9  9  2 for 1  1  5 super cell, 2  2  9 k-
point meshes for 3  3  1 super cell in sampling the Brillouin
zone by Monkhorst-Pack method, respectively. These criteria
guaranteed chemical accuracy of obtained results
satisfactorily.
Results and discussion
Geometric structure
The considered all systems have the similar crystal structure
and they are described by space group P42/mnm. In Mg4Ti2H12
and Mg8Ti2H20 system, Wyckoff positions of component ele-
ments are 2a for Ti, 4e for Mg, 4f and 8j for H, respectively.
11826 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 ) 1 1 8 2 4 e1 1 8 3 1
Wyckoff positions 2a, 4 g, 8i and 4f correspond to metal atoms,
and hydrogen atoms occupy 4f and 8i positions in Mg16Ti2H36,
Mg14Ti4H36 and Mg12Ti6H36 system, respectively.
We obtained optimized unit cells of considered systems by
relaxing initial structures. Fig. 1 shows unit cells that were
utilized in our work. Red spheres represent titanium atoms
and the smallest spheres are hydrogen atoms. The others are
magnesium atoms. All initial lattice parameters were selected
by referring to those of pure MgH2. Tables 1 and 2 contain
optimized Wyckoff positions of component elements in five
unit cells.
Substitution energy and heat of formation
In order to estimate effects of different substituting concen-
tration and configuration on material’s properties, we inves-
tigated five systems such as Mg4Ti2H12, Mg8Ti2H20, Mg16Ti2H36,
Mg14Ti4H36 and Mg12Ti6H36. The considered systems may be
represented as Mgm-xTixH2m. We calculated substitution en-
ergy Esub of the above mentioned systems for evaluating how
favorable are the different substitutions with titanium in the
Fig. 1 e Unit cells utilized for investigation. a): Mg4Ti2H12, b): Mg8Ti2H20, c): Mg16Ti2H36, d): Mg14Ti4H36, e): Mg12Ti6H36.
viewpoint of energy. Equation (1) is formula for calculating
substitution energies for considered systems, where E(M) is
total energy of M, and x and m are integral numbers,
respectively.
Esub (Mgm-xTixH2m) ¼ [E (Mgm-xTixH2m)-mE (MgH2)-xE(Ti)þ
xE(Mg)]/m (1)
Table 3 presents total energies calculated by a first princi-
ples calculation. We employed hcp unit cell for calculating
total energy of one magnesium or titanium atom in bulk
material. We also utilized cubic box for hydrogen molecule,
which has a size of 20  20  20 A3.
The substitution energies calculated by using Equation (1)
and data of Table 3 are equal to 0.581 for Mg4Ti2H12, 0.402 for
Mg8Ti2H20, 0.070 for Mg16Ti2H36, 0.130 for Mg14Ti4H36, 0.059 eV/
molecule H2 for Mg12Ti6H36 system, respectively. This result
implies that substitutions with titanium are very difficult in
Mg4Ti2H12 and Mg8Ti2H20 system. Also it may be regarded that
Mg16Ti2H36 and Mg12Ti6H36 system are formed easily from
pure MgH2 and Ti. In other hand, high substitution energy
 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 ) 1 1 8 2 4 e1 1 8 3 1 11827

Mg8Ti2H20 and Mg12Ti6H36 system, typically. We selected fermi

Table 1 e Wyckoff positions of atoms in Mg4Ti2H12,
energies as zero references in the figure. As shown from Fig. 2,
Mg8Ti2H20 and Mg16Ti2H36 system.
the considered systems have all metallic phase. In alloy hy-
Atom x y z
drides, it is known that high DOS near fermi level reflects the
Mg4Ti2H12 Mg (4e) 0.000 0.000 0.333 instability of the corresponding material [31].
Ti (2a) 0.000 0.000 0.000 Taking account for numbers of atoms in every unit cell,
H1 (4f) 0.305 0.305 0.000
Mg4Ti2H12 has a highest peak near fermi level and Mg12Ti6H36
H2 (8j) 0.314 0.314 0.333
Mg8Ti2YH20 Mg1 (4e) 0.000 0.000 0.200
has a lowest peak. This is consistent well to the result from the
Mg2 (4e) 0.000 0.000 0.600 substitution energies.
Ti (2a) 0.000 0.000 0.000 Heat of formation or dehydrogenation temperature is one
H1 (4f) 0.302 0.302 0.000 of the most important properties of HSM. They are calculated
H2 (8j) 0.307 0.307 0.200 from the following Equations (2) and (3).
H3 (8j) 0.312 0.312 0.400
Mg16Ti2YH36 Mg1 (4 g) 0.662 0.338 0.000
DH(Mgm-xTixH2m) ¼ [E (Mgm-xTixH2m)-(m-x)E (Mg)-xE(Ti)-
Mg2 (8i) 0.334 0.000 0.000
Mg3 (4f) 0.330 0.330 0.000 mE(H2)]/m (2)
Ti (2a) 0.000 0.000 0.000
H1 (4f) 0.098 0.098 0.000 Tdes ¼ DH/dS (3)
H2 (4f) 0.436 0.436 0.000
H3 (4f) 0.228 0.228 0.000 In Equation. (3), dS is increment of entropy in dehydroge-
H4 (8i) 0.101 0.000 0.000
nation process and may be approximated to be equal to the
H5 (8i) 0.102 0.000 0.000
entropy of hydrogen gas, 130.7 J/mol K. Table 4 lists the
H6 (8i) 0.436 0.000 0.000
calculated heats of formation and desorption temperatures by
Equations (2) and (3).
The heat of formation for pure MgH2 is 74.82 kJ/mol H2
Table 2 e Wyckoff positions of atoms in Mg14Ti4H36 and and it is very close to the experimental value 76.0 kJ/mol H2
Mg12Ti6H36 system. [17]. From Table 4, it is known that desorption temperature of
Atom x y z magnesium hydride was reduced considerably by substituting
Mg14Ti4H36 Mg1 (2a) 0.000 0.000 0.000 with titanium. The reduction of desorption temperature is the
Mg2 (8i) 0.331 0.000 0.000 most remarkable in Mg4Ti2H12 system, but the desorption
Mg3 (4f) 0.332 0.332 0.000 temperature is too low to utilize it for practical hydrogen
Ti (4 g) 0.665 0.335 0.000 storage. As shown from Table 4, it is predicted that Mg14Ti4H36
H1 (4f) 0.103 0.103 0.000
has the most appropriate desorption temperature for practical
H2 (4f) 0.434 0.434 0.000
HSM among the considered five systems, while this effect of
H3 (4f) 0.229 0.229 0.000
H4 (8i) 0.104 0.000 0.000 single substitution is as remarkable as the effects of co-
H5 (8i) 0.100 0.000 0.000 substitutions [32e35].
H6 (8i) 0.425 0.000 0.000 In order to avoid additional calculations, we calculated the
Mg12Ti6YH36 Mg1 (8i) 0.331 0.000 0.000 desorption energies per hydrogen molecule instead of acti-
Mg2 (4f) 0.324 0.324 0.000 vation energies. The desorption energies are 0.62 for MgH2,
Ti (2a) 0.000 0.000 0.000
0.33 for Mg4Ti2H12, 0.42 for Mg8Ti2H20, 0.55 for Mg16Ti2H36, 0.49
Ti (4 g) 0.650 0.350 0.000
H1 (4f) 0.095 0.095 0.000
for Mg14Ti4H36, 0.56 eV/H2 molecule for Mg12Ti6H36, respec-
H2 (4f) 0.434 0.434 0.000 tively. Magnitudes of the desorption energies reflect effec-
H3 (4f) 0.215 0.215 0.000 tiveness of different substitution quantitatively.
H4 (8i) 0.104 0.000 0.000 In addition to desorption temperature, single substitution
H5 (8i) 0.109 0.000 0.000 has advantage in aspects of simplifying process and less
H6 (8i) 0.423 0.000 0.000
expense as compared with co-substitution. It is very impor-
tant to search suitable substitution concentration and
configuration in the investigation for single substitution.
Table 3 e The calculated total energies of materials (Ry). Titanium atom is heavier than magnesium atom, conse-
Material Total energy Material Total energy quently MgH2 systems substituted with titanium have lower
hydrogen storage capacity than that of MgH2. The theoretical
Mg 79.3143 Mg4Ti2H12 564.9044
hydrogen weight percentages are 7.66 for MgH2, 5.90 for
Ti -116.7350 Mg8Ti2H20 -891.6788
H2 -2.3383 Mg16Ti2H36 -1545.3215
Mg4Ti2H12, 6.49 for Mg8Ti2H20, 6.96 for Mg16Ti2H36, 6.39 for
MgH2 -163.3970/2 Mg14Ti4H36 -1620.0836 Mg14Ti4H36 and 5.90 wt % for Mg12Ti6H36, respectively.
Mg12Ti6H36 -1695.0200
Bulk modulus
means low relative stability with respect to pure MgH2. So
Mg4Ti2H12 has the lowest relative stability and Mg12Ti6H36 has We calculated bulk moduli of the investigated systems and
the highest relative stability. compared them with that of pure magnesium hydride. In
We calculated electronic density of states (DOS) of the details, we evaluated bulk moduli by fitting ten total energies
investigated systems. Figs. 2e4 shows DOSs of Mg4Ti2H12, to the equation of state about solid state material. The total
11828 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 ) 1 1 8 2 4 e1 1 8 3 1

Fig. 2 e The calculated electronic DOS of Mg4Ti2H12.

Fig. 3 e The calculated electronic DOS of Mg8Ti2H20.

energies were obtained through self-consistent calculations dP dE

B0 ¼ V ; P¼ (5)
for unit cells that have different volumes. In other hand, bulk dV V0 dV
modulus is utilized as criterion for evaluating performance of
E0 and B0 represent total energy and bulk modulus of
HSM [36].
equilibrium state, respectively. The calculated bulk moduli are
In solid materials, the relationship between total energy
51.8 for pure MgH2, 63.4 for Mg4Ti2H12, 58.4 for Mg8Ti2H20, 55.8
and bulk modulus is represented as following equations.
for Mg16Ti2H36, 59.7 for Mg14Ti4H36, 67.2 GPa for Mg12Ti6H36,
    B00  respectively. This result indicates clearly that magnesium
B0 V 0 V0 V0
EðVÞ ¼ E0 þ B 1  þ  1 (4)
B00 ðB0  1Þ V V hydrides substituted with titanium have higher bulk moduli
 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 ) 1 1 8 2 4 e1 1 8 3 1 11829

Fig. 4 e The calculated electronic DOS of Mg12Ti6H36.

Table 4 e Heats of formation and desorption Table 5 e BECs of MgH2, Mg4Ti2H12 and Mg14Ti4H36 (|e|).
temperatures.
Hydride Atom BEC Atom BEC
Hydride Heat of formation (kJ/mol H2) Tdes (K)
MgH2 Mg þ1.6455 H 0.8228
MgH2 74.82 572.5 Mg4Ti2H12 Mg (4e) þ1.6503 H1 (4f) 0.8005
Mg4Ti2H12 -32.27 246.9 Ti (2a) þ1.4010 H2 (8i) -0.7751
Mg8Ti2H20 -40.89 312.9 Mg14Ti4H36 Mg1 (2a) þ1.6516 H1 (4f) 0.7346
Mg16Ti2H36 -53.50 409.3 Mg3 (8i) þ1.6511 H2 (4f) -0.8290
Mg14Ti4H36 -47.72 365.1 Mg4 (4f) þ1.6434 H3 (4f) -0.7193
Mg12Ti6H36 -54.61 417.8 Ti (4 g) þ1.3865 H4 (8i) -0.8248
H5 (8i) -0.8257
H6 (8i) -0.7833
than pure magnesium hydride and furthermore MgH2 may be
enhanced mechanically by titanium substitution. Mg8Ti2H20,
Mg16Ti2H36 and Mg14Ti4H36 system are favorable in the view- Table 5, it is straightly known that BECs of magnesium hydride
point of bulk modulus, since high mechanical strength means were changed fairly by substitution with titanium. In
large energy to prepare powder materials for practical appli- Mg4Ti2H12 system, all hydrogen atoms has remarkably
cations. Small change of bulk modulus is also necessary to reduced anionic property than pure MgH2 and BEC of titanium
guarantee stable existing of the corresponding material [36]. is much lower than that of magnesium, although BEC of
magnesium was increased slightly by titanium substitution.
Bader charge analysis Consequently, its overall bonding strengths are weakened
dramatically by substitution with titanium. This fact is well
We estimated Bader effective charges (BEC) of component consistent with the above result that Mg4Ti2H12 has too low
atoms by Bader charge calculations and investigated changes desorption temperature to be utilized for ordinary
of bonding strength owing to titanium substitution. Bader applications.
charge means charge that is contained in the Bader atomic In Mg14Ti4H36 system, the cationic property of titanium is
basin, while Bader atomic basin is defined as the region sur- much lower than that of magnesium, while many magnesium
rounded by the zero-flux surfaces of the electronic density atoms have slightly enhanced cationic property. In addition
gradient vector field [37]. Also BEC is difference between to, some hydrogen atoms have remarkably reduced anionic
number of valence electrons and Bader charge for an atom. property and the others’s anionic property is enhanced
Positive BEC corresponds to cationic property and negative slightly by titanium substitution. This situation results in
BEC to anionic property. In order to understand effect of appropriate weakening of overall bonding strength, thus
different substitution on ionic bonding strength, we compared Mg14Ti4H36 system would have proper desorption tempera-
BECs of pure MgH2 and typical systems substituted with ture for hydrogen releasing. It is supposed that weakening of
titanium. bonding strength in titanium substituted systems may be
Table 5 shows BECs of component atoms in typical systems related to titanium’s electronegativity which is lower than
such as pure MgH2, Mg4Ti2H12 and Mg14Ti4H36 system. From that of magnesium. Consequently, it is predicted that
11830 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 ) 1 1 8 2 4 e1 1 8 3 1
magnesium hydride may have improved desorption perfor-
mance by substituting with metal elements that have low
electronegativity.
Conclusions
In this paper, we investigated some properties of magnesium
hydrides substituted differently with titanium by a first prin-
ciples calculation. In general, high concentration of substitu-
tion induces strong destabilization in magnesium hydride,
thus hydrogen desorption temperature is decreased dramat-
ically. Also the investigation about Mg4Ti2H12 and Mg12Ti6H36
system shows that substitution configuration plays significant
role in improving performance of magnesium hydride, while
Mg4Ti2H12 has the same substitution concentration as
Mg12Ti6H36 system. Among the considered five systems,
Mg14Ti4H36 is the most favorable system in the complex
viewpoints of substitution energy, desorption temperature
and bulk modulus. Especially its ideal dehydrogenation tem-
perature is very attractive for practical applications. In the
viewpoints of desorption enthalpy and temperature,
Mg14Ti4H36 may be superior than Mg/MgH2eTiH2 or MgH2-
eTiH2 composite. Bader charge analysis demonstrated that
not only suitable substitution concentration but also config-
uration guarantees good desorption property of HSM. These
results show possibility that magnesium based hydrogen alloy
may be to have excellent performance by adjusting substitu-
tion concentration and configuration instead of co-
substitution with more than two elements.
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.
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