Journal of Materials Science & Technology 92 (2021) 148–158

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Journal of Materials Science & Technology

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Research Article

Density functional theory study on the role of ternary alloying

elements in TiFe-based hydrogen storage alloys
Won-Seok Ko a,∗, Ki Beom Park b, Hyung-Ki Park b,∗
a
School of Materials Science and Engineering, University of Ulsan, Ulsan 44610, Republic of Korea
b
Functional Materials and Components R&D Group, Korea Institute of Industrial Technology, Gangneung 25440, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: The role of additional ternary alloying elements on the performance of stationary TiFe-based hydrogen
Received 16 January 2021 storage alloys was investigated based on first-principles density functional theory calculations. As a ba-
Revised 24 March 2021
sic step for examinations, the site preference of each alloying element in the stoichiometric and non-
Accepted 24 March 2021
stoichiometric B2 TiFe compounds was clarified considering possible anti-site defects. Based on the re-
Available online 8 May 2021
vealed site preference, the effect of various possible ternary elements on the hydrogen storage was exam-
Keywords: ined by focusing on the formation enthalpies of TiFeH and TiFeH2 hydrides, which were closely related to
Hydrogen storage alloy the change in the location of plateaus in the pressure−composition−temperature curve. Several physical
Titanium-iron properties such as the volume expansion due to hydride formation were also examined to provide ad-
Density functional theory calculation ditional criteria for selecting optimum alloying conditions in future alloying design processes. Candidate
Metallic hydride alloying elements that maximize the grain boundary embrittlement due to the solute segregation were
proposed for the enhanced initial activation of TiFe-based hydrogen storage alloys.
© 2021 Published by Elsevier Ltd on behalf of Chinese Society for Metals.

1. Introduction phase), are formed [1] according to the following reactions:

2.13FeTiH0.1 (α ) + 1.001H2 → 2.13FeTiH1.04 (β ) (1)

Hydrogen is considered one of the most promising clean, re-
newable, and sustainable energy sources as it is not accompanying
any polluting and greenhouse gasses, unlike fossil fuels. An impor-
tant issue for revitalizing the hydrogen economy is the successful
control of hydrogen energy associated with its storage and trans-
portation. Among available methods, hydrogen storage and trans-
portation by metallic hydrides based on intermetallic compounds
have received great interest due to advantages such as safety. Sev-
eral requirements should be met when considering material for
hydrogen storage, but the most important requirement is whether
it enables fast and reversible hydrogenation and dehydrogenation
processes near ambient conditions with sufficient economic feasi-
bility. Among several materials suggested for hydrogen storage, in-
termetallic TiFe compounds and their alloys are one of the most
promising candidates due to their low costs and desirable hydro-
gen absorption and desorption properties near ambient tempera-
ture and under mild pressure conditions [1-3]. If hydrogen inter-
acts with the intermetallic TiFe compound, hydrides at two dif-
ferent compositions, e.g., TiFeH∼1.0 (β phase) and TiFeH∼2.0 (γ
∗
Corresponding author.
E-mail addresses: wonsko@ulsan.ac.kr (W.-S. Ko), mse03@kitech.re.kr (H.-K.
Park).
2.20FeTiH1.04 (β ) + 0.932H2 → 2.13FeTiH1.95 (γ ) (2)
This alloy system is especially well suited for stationary applica-
tions due to its excellent reversible hydrogen storage capacity per
unit volume; therefore, its properties have been actively investi-
gated in both experimental and theoretical works [4-10].
Despite the many advantages, a major drawback of this alloy
system is its poor activation performance, which must be over-
come for practical applications [11, 12]. During the manufactur-
ing process in air, TiFe-based alloys usually suffer from poisoning
problems by gaseous elements such as oxygen. Because this be-
havior significantly degrades the hydrogen sorption property, an
additional activation treatment is required for a long time at a
high temperature under a hydrogen atmosphere. Several attempts
have been made to overcome this difficulty. For example, mechan-
ical treatments such as severe deformation [13] and ball milling
[14] were performed to improve the hydrogenation properties of
TiFe alloys [15–17]. However, the quantity of materials that can be
treated by those special processes is greatly limited, and the price
of final products is increased by additional processing. Alternately,
there have been efforts to enhance the initial hydrogen sorption
property by including additional alloying elements other than Ti
and Fe. For example, the substitution of the constituent elements

https://doi.org/10.1016/j.jmst.2021.03.042
1005-0302/© 2021 Published by Elsevier Ltd on behalf of Chinese Society for Metals.
W.-S. Ko, K.B. Park and H.-K. Park Journal of Materials Science & Technology 92 (2021) 148–158

Table 1
Dimensions of supercells and corresponding k-point meshes used in the present DFT calculations.

Structure Purpose Number of atoms Dimension of a perfect stoichiometric compound (Å) k-points

TiFe (B2) Solution energy, Site preference 128 11.796 × 11.796 × 11.796 4 × 4 × 4
TiFe (B2) GB segregation, GB embrittlement 50 7.224 × 20.46∗ × 4.171 4 × 1 × 6
TiFe (B2) Enthalpy of hydride formation 8 4.171 × 5.898 × 4.171 9 × 7 × 9
TiFeH Enthalpy of hydride formation 12 4.263 × 5.797 × 4.548 9 × 7 × 9
TiFeH2 Enthalpy of hydride formation 16 6.109 × 7.024 × 2.768 6 × 5 × 13
∗
The dimension of the supercell including the vacuum region is 33.46 Å.

(Ti and Fe) by ternary alloying elements (Al, Co, Cu, Cr, Fe, Mn, Mo,
Ni, Pd, V, Zr [18–27]) and mish-metals [28, 29] has been investi-
gated in hopes of improving the hydrogen sorption and diffusion
properties of surface oxides.
However, the selection of alloying elements in previous works
was quite arbitrary and was not the result of a systematic analysis.
In fact, the addition of alloying elements can significantly change
other important properties of TiFe-based hydrogen storage alloys,
such as hydrogen sorption and desorption pressures of TiFeH and
TiFeH2 hydrides. Besides, there may be other alloying conditions
that are much more effective than previously explored conditions
for the overall performance of hydrogen storage. Therefore, more
in-depth analyses on the effects of various alloying elements in
TiFe-based alloys are required to optimize alloying conditions for
the best performance of hydrogen storage. On the theoretical side,
the first-principles density functional theory (DFT) calculation is
effective in exploring the roles of various additional elements that
are not readily accessible by usual experimental studies. For in-
stance, the effect of ternary elements on the enthalpy of hydride
formation, which is a key quantity for the control of pressure and
temperature conditions of the hydrogen storage alloys, is readily
accessible by DFT calculations. In previous studies [30], DFT cal-
culations were successfully used to examine the enthalpy of for-
mation for TiFeH and TiFeH2 hydrides based on the total energy
Fig. 1. Atomic structure of a B2 TiFe-based bi-crystal cell associated with the
calculation of atomic configurations.  3(111)[11̄0] STGB used in the present DFT calculations for GB-related properties
The present study aims to provide crucial information to guide (the solute-GB binding energy and the GB decohesion). Atomic sites for the substi-
the design of stationary TiFe-based hydrogen storage alloys by tution of Ti and Fe atoms are denoted by numbers (Ti0, Ti1, Ti2, Fe0, Fe1).
considering various ternary alloying elements. Extensive DFT cal-
culations were performed to provide a large database that can
be utilized for future investigations. We examined the formation
riety of possible ternary elements in the TiFe alloy (Al, As, Ba, Be,
enthalpies of TiFeH and TiFeH2 hydrides to evaluate the effect
Ca, Cd, Ce, Co, Cr, Cs, Cu, Ga, Ge, Hf, K, La, Li, Mg, Mn, Mo, Na,
of ternary alloying elements on the location of plateaus in the
Nb, Ni, P, Pd, Rb, Rh, Ru, S, Sc, Se, Si, Sr, Ta, Tc, V, W, Y, Zn and
pressure−composition−temperature (PCT) curve. In addition, sev-
Zr) were considered in the present calculations using the recom-
eral physical features such as the site preference, the solution en-
mended pseudo potentials in the VASP library. Only possible sub-
ergy, the segregation tendency to grain boundary (GB), and the GB
stitutional alloying elements in the TiFe alloy were considered be-
decohesion tendency of alloying elements were examined to pro-
cause interstitial alloying elements can cause an unintended degra-
vide further selection criteria for the future design process of TiFe-
dation of the hydrogen diffusion and the hydrogen storage proper-
based hydrogen storage alloys. Especially, alloying elements that
ties by affecting the occupation of interstitial hydrogen. Magnetism
maximize the grain boundary embrittlement were suggested for
was included by considering spin-polarized calculations except for
the enhanced activation of hydrogen storage alloys.
atomic configurations with the GB.
To investigate the GB segregation and decohesion tendencies,
2. Methodology a representative GB configuration was selected for the TiFe stoi-
chiometric compound. The selected GB is  3(111)[11̄0] symmet-
The present DFT calculations were performed using the VASP rical tilt GB (STGB), where the plane normal to GB, the axis for
code [31–33] and the projector-augmented wave (PAW) method rotation of grains, and the misorientation angle are (111), [11̄0],
[34] within the Perdew-Burke-Ernzerhof generalized gradient ap- and 109.5°, respectively. This STGB was selected because it can be
proximation (GGA) [35] for the exchange-correlation functional. made small enough to be used in the DFT calculation, and it ex-
Cutoff energy of 400 eV for the plane-wave basis set and the hibits similar GB energy and segregation trends to those of usual
Methfessel-Paxton smearing method with a width of 0.1 eV were high-angle GBs [36, 37]. In the present calculation, a bi-crystal con-
used. Brillouin-zone integrations were performed for suitably large figuration consisting of 50 atoms with the  3(111)[11̄0] STGB was
sets of  -centered k-point meshes of each supercell as summarized used as shown in Fig. 1.
in Table 1. If not designated, all calculations were performed con- Initially, a bi-crystal cell consisting of only Ti and Fe atoms was
sidering full relaxation of atomic positions and cell shapes. Dur- obtained by performing a possible rigid-body translation of each
ing the ionic relaxation, criteria for the convergence of energy and grain along with lateral directions of the GB. The most stable cell
forces were set to 10−6 eV and 10−2 eV/Å, respectively. A wide va- with the minimum energy was then selected and used for further

149
W.-S. Ko, K.B. Park and H.-K. Park Journal of Materials Science & Technology 92 (2021) 148–158

Table 2
Lattice constants (a, b, c), the formation energy (Ef ) of the B2 compound, the formation energies (Ef ) of hydrides per one mol of H2 (Eqs. (7)–(9)),
and the unit cell volume obtained by the present DFT calculations as compared with reported experimental and DFT results. Results for the B2 TiFe
compound and hydrides (TiFeH and TiFeH2 ) are presented.

Compound Space group Site Atomic position Property Experiment DFT DFT(Present)
c
TiFe (B2) Pm3̄m Fe (1a) (0, 0, 0) Lattice constants, a (Å) 2.972 2.945 f , 2.9437 g 2.949
Ti (1b) (0.5, 0.5, 0.5) Unit cell volume (Å3 ) 26.25 c
25.54 f , 25.51 g 25.65
Ef ∗ (kJ/gram-atom) −40.60
TiFeH P2221 Fe (2c) (0, 0.206, 0.25) a Lattice constants, a (Å) 2.956 d 2.889 f , 2.909 g
2.898
Ti (2d) (0.5, 0.25, 0.75 a Lattice constants, b (Å) 4.543 d 4.529 f , 4.507 g
4.548
H (2a) (0, 0, 0) a Lattice constants, c (Å) 4.388 d 4.264 f , 4.284 g
4.263
Unit cell volume (Å3 ) 58.93 d 55.79 f , 56.17 g
56.19
Ef (kJ/mol H2 ) −28.1 e −25.28 f −23.08
TiFeH2 Cmmm Fe (4i) (0, 0.288, 0) b Lattice constants, a (Å) 7.029 b 6.957 f , 6.962 g
7.024
Ti (4 h) (0.2232, 0, 0.5) b Lattice constants, b (Å) 6.233 b 6.071 f , 6.121 g
6.109
H1 (4e) (0.25, 0.25, 0) b Lattice constants, c (Å) 2.835 b 2.769 f , 2.795 g
2.768
H2 (2c) (0.5, 0, 0.5) b Unit cell volume (Å3 ) 124.2 b 117.0 f , 119.1 118.8
H3 (2a) (0, 0, 0) b Ef (kJ/mol H2 ) −33.7 – −31.0 e
−26.86 f −26.09
∗
Reference states are hcp Ti and bcc Fe.
a
Previous experimental value from Ref. [54].
b
Previous experimental value from Ref. [48].
c
Previous experimental value from Ref. [42].
d
Previous experimental value from Ref. [47].
e
Previous experimental value from Ref. [1].
f
Previous DFT calculation result from Ref. [30].
g
Previous DFT calculation result from Ref. [55].

investigations. A vacuum region of at least 13 Å was presented in
the direction normal to the GB normal direction (y-direction in
Fig. 1) with periodic boundary conditions for all directions, thereby
introducing uppermost and lowermost free surface regions into the
bi-crystal cell. The dimensions of the cell along directions parallel
to the GB were fixed based on a calculated lattice constant of the
bulk TiFe stoichiometric compound. The atomic positions of two
outermost layers for both free surface regions were fixed during
the simulation. These constraints were indispensable to examine
the GB-related properties in a bulk-like environment using a lim-
ited size of DFT supercells. The bi-crystal cell with an optimized
GB structure was finally obtained by minimizing the stress applied
in the direction of the GB normal (y-direction in Fig. 1). This was
done by relaxing positions of atoms except for those in the fixed
boundary regions and adjusting the dimension of the supercell in
the direction of the GB normal. The total energy values of selected
configurations, which adjust the cell dimension along the direction
normal to the GB, were obtained in a functional form of that di-
mension. A configuration with minimum total energy was finally
selected as the equilibrium GB configuration.
To gain insight into how ternary alloying elements affect the GB
decohesion tendency, the charge density difference (CDD) was an-
alyzed. We considered the bonding charge density (ρ ) [38–40],
defined as the difference between the electron density of a self-
consistent calculation and the electron density associated with un-
bound atoms of a non-self-consistent calculation [16,17]. To ana-
lyze the characteristic of the atomic bonds, isosurface structures
with different values of ρ are visualized using VESTA [41].
3. Results and discussion
3.1. Physical properties of the stoichiometric tife compound and
hydrides
To obtain a reference for investigating the influence of alloying
elements on the properties related to hydrogen storage, it is help-
ful to analyze the properties of the stoichiometric TiFe compound
and hydrides. We first examined the lattice constants and the en-
thalpy of hydride formation as listed in Table 2. The equiatomic
TiFe compound exhibits a CsCl-type (B2) structure corresponding
to the P m3̄m (221) space group, where Ti and Fe atoms occupy the
cube corner and the center. The lattice constant of the stoichio-
metric B2 TiFe compound obtained by the present DFT calculation
at 0 K is 2.949 Å, which is in sufficient agreement with the re-
ported experimental result of 2.972 Å at room temperature [42]. At
the initial stage of hydrogen storage before the formation of metal-
lic hydrides, hydrogen atoms occupy the interstitial site of the B2
TiFe compound. Based on the present DFT calculation, it was ex-
pected that the preferred interstitial site of hydrogen is the octahe-
dral site rather than the tetrahedral site, which is consistent with
previous DFT results [43]. That is, a configuration with a hydrogen
atom located at the octahedral site is more stable than that with a
hydrogen atom located at the tetrahedral site. The octahedral site
in the B2 TiFe compound is distinguished into two different sites
depending on the configuration of surrounding atoms. One site is
surrounded by 4 Ti and 2 Fe atoms (Ti4Fe2), and the other site is
surrounded by 2 Ti and 4 Fe atoms (Ti2Fe4). Therefore, we exam-
ined the solution energy of a hydrogen atom located in these sites
as follows:
Esol = ETi64 Fe64 H1 − ETi64 Fe64 − 0.5EH2 (3)
As listed in Table 3, hydrogen prefers the site surrounded by
4 Ti and 2 Fe atoms (Ti4Fe2), which is associated with a smaller
volume expansion due to the presence of hydrogen compared to
the other configuration. This result is consistent with previous DFT
results on the B2 TiFe compound [43-46].
The TiFe alloys with equiatomic and nearly equiatomic compo-
sitions involve the formation of two hydrides at different hydrogen
concentrations, e.g., TiFeH (β phase) and TiFeH2 (γ phase) [1]. The
TiFeH hydride exhibits an orthorhombic symmetry corresponding
to P 2221 (space group 17) [47]. The TiFeH2 hydride exhibits an or-
thorhombic symmetry corresponding to Cmmm (space group 65)
[48]. The TiFeH hydride corresponds to a structure where hydro-
gen atoms occupy the more stable octahedral sites (Ti4Fe2) of the
B2 TiFe compound [44]. The TiFeH2 hydride corresponds to a struc-
ture where hydrogen atoms occupy both kinds of octahedral sites
(Ti4Fe2 and Ti2Fe4) [44]. Details of the crystal structures and cal-
culated lattice constants of B2 TiFe compound and TiFe-based hy-
drides (TiFeH and TiFeH2 ) are summarized in Table 2. The present
DFT calculation exhibits a sufficient accuracy in reproducing the
structural parameters of both hydrides as they are in fairly good
agreement with the reported experimental values. For the TiFeH

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W.-S. Ko, K.B. Park and H.-K. Park
Table 3
The solution energy (Eq. (3)) and the volume expansion due to the presence of an H atom on each interstitial site obtained by the present DFT
calculations.
Property Octahedral site (surrounded by 4 Ti and 2 Fe atoms)
Solution energy (eV) 0.203
Volume expansion by H (%) 0.149
hydride, the calculated unit cell parameters a, b and c deviated
from the experimental values by 2.0%, 0.1% and 2.8%, and for the
TiFeH2 hydride, they deviated by 0.1%, 2.0% and 2.4%, respectively.
We further examined the formation energy of the TiFe-based
hydrides (TiFeH and TiFeH2 ) considering the following partial and
total hydrogenation reactions:
2TiFe + H2 → 2TiFeH(partial hydrogenation )
2TiFeH + H2 → 2TiFeH2 (partial hydrogenation )
TiFe + H2 → TiFeH2 (total hydrogenation )
The formation energies of hydrides corresponding to these re-
actions are expressed as follows:
Efpartial (TiFeH ) = 2ETiFeH − 2ETiFe − 1EH2
Efpartial (TiFeH2 ) = 2ETiFeH2 − 2ETiFeH − 1EH2
Eftotal (TiFeH2 ) = 1ETiFeH2 − 2ETiFe − 1EH2
In these equations, all the calculated values were defined to
represent the formation energy per one mol of H2 gas for a direct
comparison between different reactions. For the reference energy
of H2 , the entropy term was neglected as it was approximated to
the energy of a H2 molecule in vacuum at 0 K. Therefore, the de-
termined formation energies do not exactly match the actual for-
mation energies at finite temperatures, but the relative differences
indicate that they provide a good approximation. The calculated
formation energies of the stoichiometric TiFe-based hydrides are
listed in Table 2. The present DFT calculation reproduces an exper-
imental trend in the relative stability between both hydrides, i.e.,
a more negative formation energy of the TiFeH2 hydride than that
of the TiFeH hydride. Sufficient agreement between the calculated
and the experimental values indeed demonstrates that the present
DFT calculation can be further used to examine the effect of vari-
ous ternary elements on the properties of the TiFe-based hydrogen
storage alloys.
3.2. Site preference of ternary elements in the tife-based hydrogen
storage alloys
The preference of an alloying element to go to the Ti or Fe
sublattice site must be identified before examining the change in
physical properties of the TiFe-base hydrogen storage alloys due to
the addition of ternary elements. To examine the site preference
of ternary elements in stoichiometric compounds, the standard de-
fect formation energies [49] associated with the substitution of a
Ti site (EX→Ti site ) and a Fe site (EX→Fe site ) were calculated based
on DFT calculations of 4 × 4 × 4 supercells with 128 atoms using
the following equations:
EX→Ti site = [(E (Ti63 X1 Fe64 ) + ETi ) − (E (Ti64 Fe64 ) + EX )]
EX→Fe site = [(E (Ti64 Fe63 X1 ) + EFe ) − (E (Ti64 Fe64 ) + EX )]
Here, E (Ti63 X1 Fe64 ) is the energy of a supercell with the substi-
tution of a Ti site by the element X, Ti64 Fe63 X1 is the energy of a
supercell with the substitution of a Fe site by the element X, and
EX is the atomic energy of element X. The reference states for the
Journal of Materials Science & Technology 92 (2021) 148–158
Octahedral site (surrounded by 2 Ti and 4 Fe atoms)
1.102
0.211
atomic energies of pure Ti, Fe, and element X are hcp, bcc, and a
single atom, respectively. Then, the site preference of alloying el-
ements can be determined by the difference between the defect
formation energies of each substitution site as follows:
ETi site→Fe site = EX→Fe site − EX→Ti site (12)
Table 4 lists the calculated standard defect formation energies
(4)
and the resulting site preferences for selected alloying elements.
Although results obtained by the standard defect formation en-
(5)
ergy are generally applicable, this method has a weakness that the
prediction is critically dependent on the arbitrary choice of refer-
(6)
ence states for constitutive Ti and Fe. This issue is even more crit-
ical if one wants to predict the site preference of ternary elements
in non-stoichiometric compounds. If the composition of the target
compound significantly deviates from the stoichiometric composi-
(7) tion, existing defects in the ordered structure play a decisive role in
the site occupation of alloying elements. For example, if the Ti-rich
(8)
B2 compound (or Fe-rich B2 compound) is stable, a certain propor-
tion of anti-site defects or vacancies in the Fe sublattice (or the Ti
(9)
sublattice) must be present. Then, the site preference of ternary al-
loying elements can be driven by competition with those defects.
The contribution by the vacancies is expected to be considerable
only at very high temperatures, where the equilibrium concentra-
tion of vacancies remains high. Instead, the presence of anti-site
defects is expected to account for the non-stoichiometric composi-
tion of the ordered B2 alloy under usual conditions. We thus ex-
amined the site preference of ternary alloying elements by com-
paring the formation energies of competing configurations of the
same composition using the following equations:
(Ti−rich )
ETi site→Fe site
= Ef [(Ti64 ), (Fe63 X1 )] − Ef [(Ti63 X1 ), (Fe63 Ti1 )]
(13)
(Fe−rich )
ETi site→Fe site
= Ef [(Ti63 Fe1 ), (Fe63 X1 )] − Ef [(Ti63 X1 ), (Fe64 )]
(14)
In Eq. (13), Ef [(Ti64 ), (Fe63 X1 )] is the formation energy of a
Ti-rich supercell formed by the substitution of a Fe site by a X
atom (Fe63 X1 ). Ef [(Ti63 X1 ), (Fe63 Ti1 )] is the formation energy of
another Ti-rich supercell with the same composition formed by the
substitution of a Ti site by an X atom (Ti63 X1 ) and the substi-
tution of a Fe site by an anti-site Ti atom (Fe63 Ti1 ). In Eq. (14),
Ef [(Ti63 X1 ), (Fe64 )] is the formation energy of a Fe-rich super-
cell formed by the substitution of a Ti site by an X atom (Ti63 X1 ).
Ef [(Ti63 Fe1 ), (Fe63 X1 )] is the formation energy of another Fe-rich
supercell with the same composition formed by the substitution of
a Fe site by an X atom (Fe63 X1 ) and the substitution of a Ti site
by an anti-site Fe atom (Ti63 Fe1 ). The formation energy of each
configuration was obtained using the following equation:
Ef = E (Tia Feb Xc ) − aE (Ti ) − bE (Fe ) − cE (X ) (15)
(10)
By combining Eqs. (13-15), the composition-dependent site
preference can be calculated using only the total energies of the
(11)
defect configurations as follows:
(Ti−rich )
ETi site→Fe site
= E [(Ti64 ), (Fe63 X1 )] − E [(Ti63 X1 ), (Fe63 Ti1 )] (16)
(Fe−rich )
ETi site→Fe site
= E [(Ti63 Fe1 ), (Fe63 X1 )] − E [(Ti63 X1 ), (Fe64 )] (17)
151
W.-S. Ko, K.B. Park and H.-K. Park Journal of Materials Science & Technology 92 (2021) 148–158

Table 4
The site preference of additional alloying elements in the B2 TiFe compound obtained from the standard defect formation energy Eqs. (10)-((12)) and the defect formation
energy based on non-stoichiometric compounds Eqs. (16)-((18)). The reference states for the atomic energies of pure Ti, Fe, and element X are hcp, bcc, and a single atom,
respectively. Previous predictions of the site preference via the Bozzolo–Ferrante–Smith (BFS) method [51] (in parentheses) are compared to the present results.

Standard defect formation Defect formation energy based on non-stoichiometric compounds

energy (eV) (eV) Site preference
Average (Ti−rich ) (Fe−rich )
ETi site→Fe site ETi site→Fe site
ETi site→Fe site
ETi site→Fe site
Equiatomic alloy Ti-rich alloy Fe-rich alloy

Al 1.039 0.771 −0.682 2.224 Ti site Fe site (Fe site) Ti site (Ti site)
As 0.228 −0.018 −1.455 1.418 Fe site Fe site Ti site
Ba 1.484 1.652 −0.202 3.507 Ti site Fe site Ti site
Be −0.032 −0.334 −1.842 1.173 Fe site Fe site Ti site
Ca 1.647 1.366 −0.128 2.859 Ti site Fe site Ti site
Cd 0.711 0.439 −1.047 1.924 Ti site Fe site Ti site
Ce 2.036 2.185 0.241 4.130 Ti site Ti site Ti site
Co −1.335 −1.621 −3.089 −0.154 Fe site Fe site (Fe site) Fe site (Fe site)
Cr −0.959 −1.189 −2.765 0.387 Fe site Fe site (Fe site) Ti site (Ti site)
Cs 0.788 0.981 −0.997 2.958 Ti site Fe site Ti site
Cu −0.321 −0.613 −2.145 0.920 Fe site Fe site Ti site
Ga 0.539 0.209 −1.311 1.729 Ti site Fe site (Fe site) Ti site (Ti site)
Ge 0.526 0.205 −1.294 1.705 Ti site Fe site Ti site
Hf 2.550 2.343 0.883 3.803 Ti site Ti site (Fe site) Ti site (Ti site)
K 0.657 0.380 −1.121 1.880 Ti site Fe site Ti site
La 2.043 1.719 0.366 3.072 Ti site Ti site Ti site
Li −0.177 −0.464 −2.003 1.075 Fe site Fe site Ti site
Mg 0.965 0.671 −0.822 2.163 Ti site Fe site Ti site
Mn −1.089 −1.362 −2.882 0.158 Fe site Fe site Ti site
Mo −0.611 −0.830 −2.387 0.727 Fe site Fe site (Ti site) Ti site (Ti site)
Na 0.208 −0.029 −1.575 1.518 Fe site Fe site Ti site
Nb 0.947 1.211 −0.709 3.132 Ti site Fe site (Ti site) Ti site (Ti site)
Ni −1.115 −1.414 −2.911 0.082 Fe site Fe site (Fe site) Ti site (Ti site)
P 0.083 −0.161 −1.608 1.285 Fe site Fe site Ti site
Pd −0.901 −1.209 −2.693 0.274 Fe site Fe site Ti site
Rb 0.693 0.419 −1.051 1.888 Ti site Fe site Ti site
Rh −2.060 −2.371 −4.172 −0.886 Fe site Fe site Fe site
Ru −2.416 −2.694 −3.857 −1.2167 Fe site Fe site (Fe site) Fe site (Fe site)
S −1.005 −1.250 −2.695 0.196 Fe site Fe site Ti site
Sc 2.101 1.847 0.396 3.299 Ti site Ti site Ti site
Se −0.364 −0.604 −2.044 0.837 Fe site Fe site Ti site
Si 0.777 0.518 −0.918 1.953 Ti site Fe site (Ti site) Ti site (Ti site)
Sr 1.761 1.428 −0.111 2.966 Ti site Fe site Ti site
Ta 1.591 1.445 −0.068 2.957 Ti site Fe site (Ti site) Ti site (Ti site)
Tc −1.868 −2.136 −3.654 −0.617 Fe site Fe site Fe site
V 0.569 0.820 −1.104 2.745 Ti site Fe site (Fe site) Ti site (Ti site)
W 0.007 −0.151 −1.653 1.350 Fe site Fe site (Ti site) Ti site (Ti site)
Y 2.386 2.146 0.693 3.599 Ti site Ti site Ti site
Zn 0.262 0.481 −1.527 2.488 Ti site Fe site Ti site
Zr 2.242 2.513 0.577 4.449 Ti site Ti site (Fe site) Ti site (Ti site)

Results obtained from Eqs. (16) and (17) indicate the site pref-
erences predicted for the non-stoichiometric Ti-rich and Fe-rich
B2 compounds, respectively. For example, a negative value from
Eqs. (16) and (17) means that the alloying element prefers the Fe
site rather than the Ti site for the substitution, and vice versa. Even
though Eqs. (16) and (17) were derived for the non-stoichiometric
compounds, the averaging of quantities obtained by both equations
provides an additional criterion to determine the site preference of
the stoichiometric B2 compound as follows:
 
Average ( Ti−rich ) (Fe−rich )
ETi site→Fe site
= ETi site→Fe site
+ ETi site→Fe site
/2
This equation provides estimates similar to Eq. (12), but it is
more advantageous because the results are independent of the
choice of reference states for Ti and Fe. Finally, determined defect
formation energies and resulting site preferences for ternary alloy-
ing elements are listed in Table 4.
By comparing different predictions of the equiatomic alloy
based on the standard defect formation energy (Eq. (12)) and
the defect formation energy of non-stoichiometric compounds
(Eq. (18)), there is general agreement between both predictions,
but with inconsistencies present in As, Na, P and W. These ele-
ments commonly indicate defect formation energies close to zero,
implying that these elements do not strongly favor a single kind of
sub-lattice site in practical B2 TiFe compounds. If we distinguish
the site preferences of these elements, even considering small en-
ergy differences, the standard defect formation energy cannot pro-
vide consistent information because the prediction critically de-
pends on the choice of reference states for Ti and Fe. There-
fore, we focused on the defect formation energy based on non-
stoichiometric compounds (Eq. (18)) to determine the site prefer-
ences of the equiatomic alloy in further investigations.
Table 4 also lists the site preferences of ternary alloying ele-
ments in the B2 TiFe with non-stoichiometric Ti-rich and Fe-rich
(18) compositions. At first glance, the site preference for the Fe-rich
compound may seem impractical because the binary phase dia-
gram of the Ti-Fe system shows significant off-symmetric solubil-
ity limits of the B2 compound for only Ti-rich compositions [50].
However, a recent experiment on Ti-Fe-V hydrogen storage alloys
[27] reported that a B2 compound with a significant Fe-rich com-
position (Ti: 46.0, Fe: 49.5, V: 4.5 at.%) can be obtained by adding
5 at.% V to a Fe-rich alloy (Ti45 Fe50 V5 ). This implies that the solu-
bility limits of the B2 compound can be extended to the Fe-rich re-
gion by adding relevant ternary alloying elements. We thus present
results for the Fe-rich composition as well as those for the Ti-rich
and equiatomic compositions in Table 4.
We also compared our results with previous theoretical re-
sults via the Bozzolo–Ferrante–Smith (BFS) method [51]. Simi-

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Table 5
The role of additional alloying elements on the formation energies (Ef ) of hydrides (TiFeH and TiFeH2 ) per one mol of H2 and the volume expansion (V ) considering
partial Eqs. (7) and ((8)) and total (Eq. (9)) hydrogenation reactions obtained by the present DFT calculations. The results for stoichiometric hydrides without alloying
elements are highlighted in bold. Underlined values indicate that the results correspond to the investigated site preference of each alloying element in the equiatomic TiFe
compound (Table 4).

Ti site Fe site
Ef (kJ / mol H2 ) V (%) Ef (kJ / mol H2 ) V (%)
Element TiFeH TiFeH2 TiFeH2 TiFeH TiFeH2 TiFeH2 TiFeH TiFeH2 TiFeH2 TiFeH TiFeH2 TiFeH2
(partial) (partial) (total) (partial) (partial) (total) (partial) (partial) (total) (partial) (partial) (total)

– −23.08 −29.11 −26.09 9.55 5.68 15.77 −23.08 −29.11 −26.09 9.55 5.68 15.77
Al −1.15 12.85 5.85 10.74 6.19 17.60 −35.21 −22.74 −28.98 7.56 6.46 14.51
As 7.71 65.09 36.40 13.78 7.55 22.36 −6.51 −16.68 −11.59 7.28 10.76 18.82
Ba −100.74 −77.01 −88.88 18.95 4.45 24.24 −15.23 −112.25 −63.74 8.90 3.06 12.23
Be −27.15 0.47 −13.34 11.84 5.79 18.32 −36.07 −23.35 −29.71 8.76 6.11 15.41
Ca −89.99 −53.15 −71.57 10.65 4.11 15.19 −64.82 −81.93 −73.37 12.11 4.63 17.29
Cd −44.52 3.36 −20.58 10.25 4.47 15.17 −42.48 −42.49 −42.48 7.72 5.35 13.48
Ce −49.59 −43.23 −46.41 9.44 5.04 14.96 −17.33 −109.08 −63.21 5.41 8.36 14.21
Co −53.48 −32.17 −42.82 10.99 6.22 17.90 −35.39 −32.92 −34.16 8.77 5.70 14.97
Cr −28.02 −38.18 −33.10 9.54 5.65 15.73 −41.24 −40.02 −40.63 9.95 4.63 15.03
Cs −90.03 −138.34 −114.18 26.91 11.14 41.05 −9.12 −125.15 −67.13 7.50 7.27 15.32
Cu −40.42 −24.10 −32.26 9.46 6.65 16.74 −49.15 −34.29 −41.72 8.79 5.56 14.83
Ga 0.76 23.90 12.33 12.81 5.07 18.53 −29.21 −17.64 −23.42 8.14 6.29 14.94
Ge 32.03 45.10 38.56 12.68 6.87 20.43 −17.04 −9.02 −13.03 6.46 7.72 14.68
Hf −30.13 −19.55 −24.84 8.97 5.11 14.54 −39.24 −85.56 −62.40 7.69 7.51 15.77
K −106.50 −115.16 −110.83 5.84 11.38 17.88 −65.48 −126.07 −95.78 3.25 6.32 9.77
La −72.21 −40.53 −56.37 14.40 1.49 16.10 −26.09 −97.55 −61.82 7.84 4.41 12.60
Li −77.83 −50.22 −64.03 9.57 6.03 16.18 −59.87 −47.63 −53.75 9.35 6.38 16.32
Mg −59.97 −21.76 −40.86 10.01 4.77 15.25 −47.21 −48.83 −48.02 8.89 6.07 15.49
Mn −33.91 −13.51 −23.71 11.96 2.26 14.49 −28.44 −29.44 −28.94 9.82 5.51 15.87
Mo −26.58 −40.91 −33.74 8.25 5.09 13.75 −40.25 −36.07 −38.16 10.30 4.52 15.29
Na −83.74 −76.31 −80.03 4.88 12.04 17.51 −63.75 −78.32 −71.04 6.49 9.04 16.12
Nb −28.30 −33.52 −30.91 8.47 5.52 14.46 −49.44 −59.03 −54.23 10.28 4.13 14.83
Ni −36.43 −26.29 −31.36 8.07 5.92 14.47 −45.90 −34.84 −40.37 8.93 5.40 14.82
P −0.97 83.38 41.20 14.86 12.05 28.70 −4.55 −8.55 −6.55 8.11 6.88 15.55
Pd −39.05 −22.77 −30.91 7.17 4.93 12.46 −38.63 −45.90 −42.27 8.56 5.01 14.00
Rb −103.45 −136.78 −120.12 8.72 12.45 22.26 −38.26 −143.42 −90.84 4.34 7.04 11.68
Rh −21.83 −32.77 −27.30 5.15 6.30 11.78 −22.95 −36.02 −29.49 8.88 5.33 14.68
Ru −20.09 −38.83 −29.46 7.77 3.70 11.76 −8.26 −25.52 −16.89 9.50 6.08 16.16
S −60.16 54.81 −2.67 12.15 14.81 28.77 −22.86 −58.08 −40.47 10.76 12.68 24.80
Sc −48.19 −35.02 −41.61 9.84 4.73 15.03 −49.29 −75.63 −62.46 9.69 4.27 14.38
Se −35.86 46.99 5.57 12.58 12.42 26.56 −8.94 −54.24 −31.59 9.00 11.10 21.10
Si 38.64 50.98 44.81 13.01 6.15 19.95 −18.95 −6.79 −12.87 6.59 7.18 14.24
Sr −103.44 −64.03 −83.74 12.72 0.67 13.47 −47.17 −91.25 −69.21 5.29 3.99 9.49
Ta −20.10 −20.77 −20.43 8.50 5.50 14.48 −46.62 −63.54 −55.08 10.12 4.03 14.55
Tc −25.86 −43.44 −34.65 6.96 5.74 13.09 −18.53 −20.84 −19.68 9.82 5.29 15.63
V −21.51 −34.47 −27.99 9.45 5.85 15.85 −49.11 −56.59 −52.85 9.17 4.68 14.28
W −15.37 −27.02 −21.20 8.20 5.18 13.81 −39.04 −38.78 −38.91 10.52 3.93 14.87
Y −67.24 −30.27 −48.76 11.77 2.11 14.13 −41.65 −87.20 −64.42 7.01 3.76 11.03
Zn −32.10 0.05 −16.03 10.66 5.67 16.94 −38.20 −28.80 −33.50 8.75 5.74 15.00
Zr −37.61 −28.51 −33.06 8.81 4.96 14.21 −41.43 −88.91 −65.17 7.28 7.91 15.77

lar to the present method, this study [51] provided predictions
on the site preferences of several elements in various B2 com-
pounds using configurations with anti-site defects. The reported
predictions [51] considering non-stoichiometric compositions are
listed and compared to our predictions in Table 4 (in parenthe-
ses). There is general agreement between both results, but sev-
eral inconsistencies are present regarding the Ti-rich alloy. We
attribute these deviations to the different methods of obtaining
the total energy of the atomic configurations. The BFS method
[51] is a more semi-empirical calculation, as it is a quantum ap-
proximation technique based on the formation energy of the tar-
get atomic configuration, given as the sum of individual atomic
contributions.
Although comparison of our results with experimental data is
desirable, to the best of our knowledge there is an absence of di-
rect analyses of site preferences for ternary elements in TiFe alloys,
including investigations based on the atom probe tomography. Al-
ternately, we can justify our predictions in an indirect manner by
further considering the alloying effects on hydrogen storage prop-
erties, which will be discussed in the next section.
3.3. Roles of ternary elements on the hydrogen storage
In the previous section, we examined the site preference of
each alloying element in the B2 TiFe compound. In this section,
we extend the investigation to properties of the TiFe-based hy-
drides with alloying elements based on the revealed tendency of
the site preference. We analyzed the roles of ternary alloying ele-
ments on the formation energies of the TiFe-based hydrides (TiFeH
and TiFeH2 ), which are closely connected with the alteration of re-
quired pressure conditions for the hydrogen sorption and desorp-
tion processes. All calculation results were obtained using a fixed
concentration where a solute atom substitutes the Ti or Fe sublat-
tice site of a B2 supercell composed of 4 Ti atoms and 4 Fe atoms
as listed in Table 1. Therefore, the present DFT calculations only
provide overall trends for the change in formation energies as each
ternary alloying element is added, and the estimates do not corre-
spond to the exact composition that can be practically realized.
Table 5 lists the calculated formation energies of the TiFe-
based hydrides with a ternary alloying element. The results for
the stoichiometric TiFeH and TiFeH2 compounds without any so-

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Table 6
The role of additional alloying elements in altering the plateau hydrogen pressure in the PCT curve. The predictions according to the present DFT calculations in Tables 4
and 5 are compared to the previous predictions via the Bozzolo–Ferrante–Smith (BFS) method [51] and previously reported experimental trends. The results for different
compound stoichiometries (Equiatomic, Ti-rich, and Fe-rich) are specified. “Stabilized” and “Destabilized” indicate a decrease and increase in the plateau hydrogenation
pressure, respectively.

Experiment Present prediction Prediction by BFS method [51]

Element Stoichiometry Stability of hydrides Site preference Stability of hydrides Site preference Stability of hydrides∗

Al Equiatomic Destabilized [25] Ti site Destabilized

(Ti47.5 Fe47.5 Al5 )
Co Ti-rich Stabilized [20] Fe site Stabilized Fe site Stabilized
(Ti50 Fe45 Co5 )
Co Equiatomic Stabilized [56] Fe site Stabilized Fe site Stabilized
(Ti49 Fe49 Co2 )
Cr Equiatomic Stabilized [25] Fe site Stabilized
(Ti48 Fe48 Cr4 )
Cr Ti-rich Stabilized [27] Fe site Stabilized Fe site Stabilized
(Ti47 Fe43.3 Cr9.7 ,
Ti47.1 Fe41 Cr11.9 )
Mn Ti-rich Stabilized [18] Fe site Stabilized
(Ti49 Fe46 Mn5 ,
Ti50 Fe40 Mn10 ,
Ti48 Fe40 Mn12 ,
Ti50 Fe35 Mn15 )
Nb Equiatomic Stabilized [56] Ti site Stabilized Ti site Stabilized
(Ti49 Fe49 Nb2 )
Ni Ti-rich Stabilized [20, 57] Fe site Stabilized Fe site Stabilized
(Ti50 Fe45 Ni5 ,
Ti50 Fe42.5 Ni7.5 ,
Ti50 Fe40 Ni10 )
Pd Ti-rich Stabilized [19] Fe site Stabilized
(Ti50 Fe45 Pd5 ,
Ti50 Fe40 Pd10 )
V Ti-rich Stabilized [26] Fe site Stabilized Fe site Stabilized
(Ti50 Fe47 V3 , Ti50 Fe45 V5 )
V Fe-rich Destabilized [26] Ti site Destabilized Ti site Destabilized
(Ti47 Fe50 V3 , Ti45 Fe50 V5 )
Zr Equiatomic Stabilized [58] Ti site Stabilized
(Ti45.1 Fe45.1 V9.8 )
∗
Because the BFS method [51] provided only the site preference information, alteration of the plateau hydrogen pressure is obtained based on the present calculation
results for the hydride formation energies listed in Table 5.

lute elements (Table 2) are also listed for comparison. The ob-
tained changes in the formation energy are fairly large due to a
high concentration (12.5 at.% of solute atoms in the B2 structure)
of ternary alloying elements considered in the present calculation.
Therefore, only the direction of changes, i.e., the stabilization or
destabilization of hydrides due to the addition of ternary elements
should be of interest from the present calculation results. We cal-
culated and listed all formation energies considering possible sub-
stitutions of both Ti and Fe sites. This information should be used
in conjunction with the composition of practical alloys, such as
the equiatomic, Ti-rich, or Fe-rich compositions. As an example,
we specified predictions (underlined values in Table 5) that cor-
respond to the investigated site preference of alloying elements in
the equiatomic TiFe compound (Table 4).
Then, predicted trends in the change of hydride formation en-
ergies due to ternary alloying elements are compared to reported
experimental trends. The equilibrium conditions of pressure and
temperature where material can absorb and desorb hydrogen can
be expressed by following the Van’t Hoff equation:
 
Peq H 0 S 0
ln = −
P0 RT R enthalpies of hydrides. As listed, the present results considering
Here, Peq is the plateau (or equilibrium) hydrogen pressure in
the PCT curve, P0 is the pressure at standard state (1 atm), R is
the ideal gas constant, T is the temperature, H 0 is the change
in enthalpy at standard state, and S0 is the change in entropy
at standard state. Because the entropy change associated with the
(de)hydrogenation process is similar for usual metallic hydrides
and its changes due to the substitution of alloying elements are
negligible, the equilibrium properties of various metal–hydrogen
systems are usually compared by evaluating only the enthalpy
change associated with the (de)hydrogenation process [52]. There-
fore, a decrease or increase in the plateau hydrogenation pres-
sure (Peq ) indicates that the hydride phase is stabilized (more en-
dothermic) or destabilized (more exothermic), respectively. When
neglecting the temperature dependence of the enthalpy differ-
ence of each phase, the formation energies of hydrides (Ef ) at
0 K obtained by the present DFT calculations can be approxi-
mated to be the formation enthalpy determined from the slope
(H 0 /R) of the experimental Van’t Hoff plot (logP vs. 1/T in
Eq. (19)).
The experimentally measured trends in the alteration of the
plateau hydrogen pressure in the PCT curve by the addition of
ternary elements with detailed information on the bulk compo-
sition are summarized and compared to the present results in
Table 6. It should be noted that the B2 compound composition
can deviate somewhat from the bulk composition if the mate-
rial is not composed of a single phase. In this table, “destabi-
lized” and “stabilized” indicate an increase and decrease in the
plateau hydrogenation pressure, respectively, and these trends re-
spectively correspond to the more positive and negative formation
(19)
the stoichiometry of alloying elements are consistent with the re-
ported experimental trends. In particular, it is worth noting the
predictions for the V-containing alloy system. As mentioned in the
previous section, the recent experimental study on Ti-Fe-V hydro-
gen storage alloys [27] analyzed the effects of V addition on al-
tering the plateau hydrogen pressure considering both the Ti-rich
and Fe-rich compositions of the B2 compound. The reported re-
sults showed that the addition of V to the Ti-rich B2 compound

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Table 7
The solute-GB binding energy for possible segregation sites near the GB (Ti1, Ti2, and Fe1 shown in Fig. 1) and the maximum tensile stress
(σmax ) obtained by the present DFT calculation. In the solute-GB binding energy, the most probable site for the segregation of each ternary
element considering the preferred sublattice site of the equiatomic B2 structure (Table 4) is highlighted in bold. The maximum tensile
stress was obtained using the bi-crystal cell with an additional solute atom at the most probable site near the GB.

Ti1 (eV) Ti2 (eV) Fe1 (eV) σmax (GPa)

TiFe 31.48
Al 0.037 −0.191 30.89
As 0.487 29.13
Ba 1.602 1.220 12.69
Be 0.639 26.85
Ca 1.143 0.693 18.68
Cd 0.747 0.101 27.71
Ce 1.058 0.958 23.05
Co 0.120 28.59
Cr 0.104 29.35
Cs 1.450 1.061 12.65
Cu 0.339 24.28
Ga 0.101 −0.154 29.98
Ge −0.224 −0.131 30.03
Hf 0.503 0.208 29.28
K 1.375 1.055 13.54
La 1.339 1.081 19.00
Li 0.033 18.11
Mg 0.563 0.065 28.57
Mn 0.024 31.27
Mo −0.173 28.95
Na −0.225 13.03
Nb 0.356 0.139 31.55
Ni 0.300 27.20
P 0.743 27.56
Pd −0.010 24.47
Rb 1.439 1.184 12.85
Rh −0.235 28.49
Ru −0.327 30.71
S 0.790 20.11
Sc 0.580 0.247 28.37
Se 0.565 19.10
Si −0.516 −0.246 30.46
Sr 1.414 1.072 14.98
Ta 0.190 0.049 31.67
Tc −0.301 31.28
V −0.231 −0.050 30.13
W −0.054 31.91
Y 1.104 0.679 22.46
Zn 0.334 −0.093 30.54
Zr 0.651 0.324 28.92

causes a significant decrease in plateau hydrogenation pressure,
while the addition of V to the Fe-rich B2 compound causes a slight
increase in plateau hydrogenation pressure. This is expected based
on the present calculation results for the site preference and for-
mation energies of hydrides listed in Tables 4 and 5. This com-
parison justifies the present predictions of the hydride formation
energies as well as the predictions of the composition-dependent
site preference of alloying elements, as explained in the previous
section.
In Table 5, we also provide the volume expansion due to the
hydride formation, i.e., the volume difference between the initial
B2 compound and the final hydride structures. In many metal–
hydrogen systems including the TiFe system, hysteresis in the PCT
curve is commonly presented as indicated by a higher transition
pressure during the hydrogenation process than that during the
dehydrogenation process. The origin of such hysteresis behavior
has not been fully understood, but a severe lattice expansion due
to the hydrogenation process is believed to be a possible factor
[53]. For example, the formation of hydrides is expected to cause
irreversible plastic deformation of the matrix phase. Then, the vol-
ume expansion due to the hydride formation and its alteration by
the addition of ternary elements can affect the amount of plastic
deformation and the resulting intensity of the hysteresis in the PCT
curve.
3.4. Roles of ternary elements on grain boundary embrittlement
GB embrittlement affected by the addition of ternary elements
is another factor that can be considered in the future alloying de-
sign process. GB embrittlement due to the segregation of impu-
rities is not a desirable phenomenon in usual metallic materials.
However, one can think of GB embrittlement as a possible way for
enhancing activation of hydrogen storage alloys because it can pro-
vide native surface regions without oxidation through the fracture
of initial hydrogen storage alloys with surface oxides. The virtues
of possible impurities in the TiFe alloys that should be used for
this purpose are the high segregation tendency to GB regions and
the high decohesion tendency of atomic bonds.
Even considering the same misorientation angle and axis for ro-
tation, there are two types of  3(111)[11̄0] STGB, where Ti or Fe
atoms are located at the center of the GB region. We first con-
firmed that the GB with Ti atoms in its center is more stable than
the GB with Ti atoms in its center. Therefore, we focused on the
more stable GB (Fig. 1) for further examining the segregation and
decohesion tendencies. We then examined the GB segregation ten-
dency of ternary elements in the B2 TiFe compound by examining
the binding energy between the GB and a ternary solute atom. This
binding energy is related to approximately the maximum amount
of the solute atoms near the GB region that can be induced by

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the intended pre-annealing process at relevant temperatures to en-

hance the segregation phenomenon. The binding energy between
two defects is defined as a difference in energies of two configura-
tions when defects are adjacent to each other and when they are
separated enough and non-interacting. In the present study, the
interaction energy between the  3(111)[11̄0] STGB and a ternary
solute atom placed in possible segregation sites was considered.
Those segregation sites are composed of two Ti sites (Ti1, Ti2) and
one Fe site (Fe1) near the GB region as shown in Fig. 1. Consider-
ing these sites, the binding energy between the GB and a ternary
solute atom was calculated about the configuration where a solute
atom substitutes for a Ti (Ti0) or a Fe (Fe0) site located far from
the GB region (Fig. 1). To calculate accurate binding energy values,
the minimization of the stress applied in the direction of the GB
normal (y-direction in Fig. 1) was performed after each substitu-
tion of solute atoms.
Table 7 lists the calculated binding energies between various
ternary elements and the GB. According to the definition of bind-
ing energy, a positive sign (negative sign) means that the GB and a
ternary solute atom are attracted to (repulsed by) each other. The
calculated binding energies are different for each GB site. These
values provide useful information in evaluating the most probable
site for the segregation of various ternary alloying elements near
the GB region. Among different values for each site, the most im-
portant is the largest binding energy given the preferred substitu-
tion site of each ternary alloying element, as highlighted in bold in
Table 7 (e.g., a value for the Ti1 site if Al is the allying element).
We also examined the role of ternary elements on the fracture
of the GB by performing a DFT tensile test. This method provides a
useful way to evaluate the rough embrittlement tendency focusing
on the decohesion of atomic bonds due to the addition of alloying
elements near the GB region. For the DFT tensile test, an initial bi-
crystal cell with a ternary solute atom located in the most stable
GB site (Table 7) was considered for each alloying element. After
the stable GB configuration was obtained by minimizing the stress
along the direction normal to GB (y-direction in Fig. 1), a uniaxial
tensile loading was applied along this direction by increasing the
distance between the uppermost and lowermost boundary regions
with an incremental step of 0.25 Å. Positions of all atoms except
those in the fixed boundary regions could fully relax. Dimensions
along the lateral directions of the GB were fixed during the tensile
loading to better reproduce a triaxial stress state near the crack tip
that presents in the fracture process of practical materials. After
a certain number of loading steps, the bond-breaking process and
resulting exposure of surfaces near the GB region were observed
while the simulation starts without any pre-defined fracture sur-
faces. The DFT tensile test provided a variation in the total energy
as a function of the distance between two fixed boundary regions.
The corresponding tensile stress (σ ) at a specific strain (ε ) was ob-
tained using the following equation:
1 ∂E Fig. 2. DFT calculation results for the tensile stress vs. loading distance responses
σ= (18)
(ε ) ∂ε of B2 TiFe-based bi-crystal cells with a ternary solute atom near the GB region. For
each alloying element, a bi-crystal cell with a ternary solute atom at the most prob-
Here, (ε ) is the volume and E is the total energy of the bi- able GB site (Table 7) is used for the calculation. The maximum tensile stress (GPa)
obtained from each response is represented in parenthesis. The reference response
crystal cell.
of the bi-crystal cell without ternary alloying elements is represented as “TiFe”.
The obtained relations between the tensile stress and the sepa-
ration distance of bi-crystal cells with various ternary alloying el-
ements are shown in Fig. 2. The response of a pristine bi-crystal
cell without any alloying elements is also presented for compar- elements located in their respective stable GB sites. As shown
ison. Each alloying element located near the GB region exhibited in the figure, there is a noticeable correlation between the CDD
significantly different decohesion tendencies of atomic bonds. near the ternary atom and the maximum tensile stress. Given that
Fig. 3 shows the calculated CDD of bi-crystal cells at the initial charge accumulation and depletion are direct indicators of the
stage of the tensile loading, as visualized by the isosurface struc- strengthening or weakening of atomic bonds, it is not surprising
tures with different values of ࢞ρ . We selected several ternary al- that the CDD is associated with the decohesion tendency of GBs.
loying elements that exhibit a wide range of the maximum tensile For alloying elements that exhibit relatively higher maximum ten-
stress values and compared the CDD of bi-crystal cells with those sile stress values (e.g., Nb and Mn), the CDD near a ternary atom is

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Fig. 3. The calculated charge density difference (CDD) in the (11̄0 ) plane of the  3(111)[11̄0] STGB at the initial stage of tensile loading obtained using the present DFT
calculations. GBs with a solute atom substituting the Ti site (Nb, Sc, Cd, Y, Ca, and Sr) and those with a solute atom substituting the Fe site (Mn, P, Cu, S, Li, and Na) are
presented. The values in parentheses represent the maximum tensile stresses (GPa) listed in Table 7.

similar to that of the reference TiFe GB. For other alloying elements
with lower maximum tensile stress values, there is a significant
decrease in the charge density around the ternary atom, indicating
that the atomic bonds between the ternary atom and nearby Ti or
Fe atoms become weaker compared to those of the reference TiFe
GB.
As stated above, possible ternary alloying elements in the TiFe
alloys induce GB embrittlement if they have a high tendency to
segregate to the GB region and a high tendency to exhibit deco-
hesion of atomic bonds. To identify the combination of these con-
ditions more clearly, the correlation between the solute-GB bind-
ing energy (segregation tendency) and the maximum tensile stress
(decohesion tendency) was plotted for each ternary solute element,
as shown in Fig. 4. There are several candidate ternary alloying el-
ements that can maximize the GB embrittlement behavior as high-
lighted by the shaded area in Fig. 4.
These elements are expected to contribute to the exposure of
native surfaces without oxides through enhanced GB fracture if
proper processing conditions (e.g., pre-annealing process) to en-
hance the amount of the GB segregation is considered during the
manufacturing of the TiFe-based hydrogen storage alloys. Although
Fig. 4. Relations between the solute-GB binding energy (segregation tendency) and
the suggested alloying elements satisfy the selection criteria that the maximum tensile stress (decohesion tendency) for each alloying element ob-
focused on GB embrittlement, other factors could be important tained by the present DFT calculations. Among solute-vacancy binding energy val-
considering the practical alloying design process. For example, if ues for different segregation sites of each alloying element, the maximum value
the solubility of a ternary alloying element in the B2 TiFe com- considering the predicted site preference of each element (values in bold in Table 7)
is used.
pound is extremely low, the actual amount of the GB segregation
can be much less than expected. If so, alternative alloying elements
with sufficient solubility in the B2 TiFe compound with a moder- ing conditions is beyond the scope of the current work and is left
ate GB segregation tendency could be a better choice. Moreover, in to possible future experimental investigations.
the practical alloy design process, detailed conditions for alloying
elements and target concentrations should be decided considering 4. Conclusion
their roles on other important characteristics of hydrogen storage
alloys, e.g., the enthalpy of hydride formation and the amount of The role of various ternary elements on the performance of sta-
hysteresis in the PCT curve. The derivation of such detailed alloy- tionary TiFe-based hydrogen storage alloys has been investigated

157
W.-S. Ko, K.B. Park and H.-K. Park
based on extensive DFT calculations. As a basic step for predictions,
the site preference of each alloying element in the stoichiometric
and non-stoichiometric B2 TiFe compounds has been clarified con-
sidering the formation of anti-site defects. Based on the revealed
site preference, the effects of a wide variety of possible alloying
elements have been examined by focusing on the formation en-
thalpies of TiFeH and TiFeH2 hydrides, which are closely related
to the changes in the locations of plateaus in the PCT curve. Addi-
tional physical properties such as the volume expansion due to hy-
dride formation have been also examined to provide further crite-
ria for selecting optimum alloying conditions in future alloying de-
sign processes. In particular, alloying elements that maximize the
GB embrittlement due to the solute segregation phenomenon are
proposed for enhancing the initial activation of TiFe-based hydro-
gen storage alloys.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgements
This research was supported by the National Research Founda-
tion of Korea (NRF) funded by Ministry of Science and ICT (Nos.
NRF-2019M3E6A1103984 and NRF-2019M3D1A1079214).
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