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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9

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Hydrogenation properties of nanocrystalline

TieVeMn body-centered-cubic alloys

M. Balcerzak*
Institute of Materials Science and Engineering, Poznan University of Technology, Jana Pawła II no 24, 61-138 Poznan,
Poland

article info abstract

Article history: An effect of Mn content in nanocrystalline TieVeMn alloy on hydrogenation properties has
Received 5 October 2018 been investigated systematically in this work. Ti0.5V1.5-xMnx (x ¼ 0, 0.1, 0.2, 0.3) alloys are
Received in revised form synthesized by mechanical alloying method. It has been shown that all alloys need to be
1 February 2019 activated in order to present the best hydrogenation properties. With increasing Mn con-
Accepted 11 February 2019 tent in TieVeMn alloys, the maximum hydrogen storage capacity at room temperature
Available online 8 March 2019 firstly increases to reach 3.07 wt% for Ti0.5V1.4Mn0.1 alloy and then gradually decreases.
Reversibility of hydriding-dehydriding process improves after chemical modification of
Keywords: TieV alloy. Hydrogen storage properties result from phase composition and structure of
V-based alloy alloys. All samples are composed of a major body-centered-cubic (BCC) phase. In Mn-
Nanomaterials containing materials also a second BCC phase has been detected. Its abundance
Metal hydrides increases with higher content of Mn in the alloy. Moreover, with increasing Mn content,
Thermodynamic properties the lattice parameters of both phases decrease.
Hydrogen sorption © 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
X-ray diffraction

Moreover, the use of BCC alloys is limited due to low gravi-

Introduction
Metal hydrides can store hydrogen in their solid state.
Hydrogen sorption and desorption can be performed for some
of them at a reasonable temperature and pressure (near to
ambient) [1e4]. Among many known materials, body-centered-
cubic (BCC) solid solutions are considered as one of the prom-
ising hydrogen storage alloys. It is due to their hydrogen stor-
age density which is higher than for well-known intermetallic
compounds [5e10]. BCC alloys show a total hydrogen storage
capacity of H/M ~2. Unfortunately, they are able to desorb just a
half of absorbed hydrogen (at ambient conditions) because of
low desorption pressure of monohydride phase [11,12].
metric storage density, high hydride stability and poor cyclic
stability [11]. Hydrogenation properties of BCC alloys can be
improved by use of other preparation methods, heat-treatment
and chemical modification [13,14].
An effect of partial substitution of V by Mn atoms in
Ti0.5V1.5 alloy on hydrogen storage properties has been
investigated in the present study. Addition of Mn can increase
the effective hydrogen capacity (by increasing the plateau
pressure) and strengthen the anti-oxidation and anti-
corrosion abilities of the modified alloy. Mn is also an
element that effectively improves the electrochemical
properties of Laves phase alloys used as electrode materials in
a Ni-MH secondary batteries [15,16]. V-rich BCC alloys,

* Corresponding author.
E-mail address: mateusz.balcerzak@put.poznan.pl.
https://doi.org/10.1016/j.ijhydene.2019.02.092
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
15522 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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9

moreover, suffer from the high price of V. The price of these
alloys can be reduced by substitution of expensive V atoms by
cheaper Mn atoms.
Recently, the author has reported the hydrogen storage
properties of TieV BCC alloy synthesized for the first time by
mechanical alloying (MA) method. Obtained nanocrystalline
MA BCC alloys have shown good activation properties and fast
hydrogen sorption [15]. Ball milling was also used in the past
to produce the composite material based on microcrystalline
TieVeMneCr BCC and LaNi5-type alloys. The synthesized
material was characterized by improved activation perfor-
mance which resulted from created core-shell structure [17].
Moreover, S. Couillaud et al. and J. Huot et al. used the ball
milling in order to improve hydrogenation properties of arc
melted TieVeMn alloy [11,19].
However, to the best of author' knowledge, there is no in-
formation concerning on nanocrystalline TieVeMn BCC alloys
synthesized by MA method. Moreover, in the past, TieVeMn-
type alloys were studied as Laves phase related BCC alloys and
there is no information on the structural and hydrogen storage
properties of simple TieVeMn BCC alloys [6,14,15,18e28]. For
this reason, this work is focused on studies of hydrogenation
properties of MA Ti0.5V1.5-xMnx alloys (x ¼ 0, 0.1, 0.2, 0.3). The
obtained results are discussed with reference to the current
state of knowledge.
Experimental procedure
Samples of Ti0.5V1.5-xMnx alloys (x ¼ 0, 0.1, 0.2, 0.3) were pre-
pared by MA the constituent metals under argon atmosphere
(99.5% powder Ti, 99.5% powder V, 99.95% powder Mn). MA
lasted 14h to obtain BCC alloys. Details about MA process were
included in the previous work [15]. Chemical compositions of
obtained alloys were studied by energy dispersive X-ray
spectrometer (EDS) e Tescan VEGA TS5135. The average
elemental compositions of all studied BCC alloys are listed in
Table 1. EDS data show that chemical compositions of ob-
tained alloys are not matched to expected compositions.
However, the differences between these compositions are
rather small and can be associated with the accuracy of EDS
method.
Hydrogen sorption/desorption behaviour of Ti0.5V1.5-xMnx
alloys was characterized at near room temperature by kinetic/
activation curves and pressure-composition isotherms (PCI) -
measured by a Sieverts-type device (a product of Particulate
Systems). The initial hydrogen pressure and temperature in
kinetic/activation measurements equalled 3 MPa and 303 K,
respectively. These time-composition curves were obtained
using time-pressure curves and calculated hydrogen concen-
tration. The curves were normalized by assuming that the
hydrogen concentration: equals 0 wt% in t ¼ 0; reaches
maximum value in an equilibrium state. Details concerning
these studies were included in the previous work [15].
Structural, microstructural and thermal analyses were
performed to explain the changes in hydrogen storage prop-
erties of TieVeMn alloys. The microstructure was examined by
scanning electron microscopy (SEM) e Tescan VEGA TS5135.
Micrographs were used to make particle size dimension dis-
tribution histograms. High resolution transmission electron
microscope (HRTEM) e Joel ARM 200 F was used to observe the
microstructure in details. The crystal structure and lattice pa-
rameters of MA alloys were determined by X-ray powder
diffraction (XRD) using Cu Ka radiation e Panalytical Empyrean.
XRD measurements were also performed on fully hydroge-
nated BCC alloys. Diffraction profiles were analysed by Rietveld
refinement Maud program. Williamson-Hall style plot was
used to evaluate average crystallite size and lattice strain of MA
alloys. Differential scanning calorimetry (DSC) studies were
made on fully hydrogenated samples under argon protective
gas with a constant heating rate of 10K/min e TA DSC Q20.
It should be noticed, that studied Ti0.5V1.5-xMnx alloys and
additionally synthesized Ti0.5V1.4-xNi0.1Mnx alloys have been
also tested for their usefulness as negative electrodes in Ni-
MHx secondary electrodes. The electrochemical test results
are not shown in this work because increasing Mn content
has not improved the electrochemical properties of TieV and
TieVeNi alloys. The same conclusion was also reported by
Q.A. Zhang et al. for the Laves phase related BCC alloys [15].

Table 1 e Chemical composition of samples determined Results and discussion

from materials weighted before synthesis and from EDS
measurements.
Hydrogenation properties
Sample E Wsyn (%) WEDS (%) Formula obtained
from EDS
Time-capacity curves of Ti0.5V1.5-xMnx alloys in activation/ki-
Ti0.5V1.5 Ti 23.88 24.86 Ti0.5V1.42 netic measurements are presented in Fig. 1. All of TieVeMn
V 76.12 75.14
alloys were tested without any activation. On each sample,
Ti0.5V1.4Mn0.1 Ti 23.79 24.62 Ti0.5V1.34Mn0.09
three activation/kinetic measurements were done. Samples
V 70.76 70.38
Mn 5.45 5.00 were degassed between the cycles at 673 K.
Ti0.5V1.3Mn0.2 Ti 23.69 25.59 Ti0.5V1.21Mn0.15 One of the main problems concerning the application of
V 65.45 65.73 V-rich alloys is the difficulty of their activation [6]. All of the
Mn 10.86 8.68 tested samples are in an inactive state in the first cycle. The
Ti0.5V1.2Mn0.3 Ti 23.60 26.93 Ti0.5V1.04Mn0.22 inactive state of studied alloys is most likely associated with a
V 60.18 59.68
surface oxide layer which restrains the hydrogen sorption
Mn 16.22 13.39
reaction [29,30].
E  element. However, the activation of alloys investigated in this paper
Wsyn - weight before synthesis.
does not seem to be a problem. All alloys have shown the best
WEDS - weight based on EDS.
or nearly the best hydrogenation kinetics just after one cycle
 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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9
Fig. 1 e Time-capacity curves of Ti0.5V1.5-xMnx alloys in
activation/kinetic measurements (3 MPa of initial
hydrogen pressure, 303 K). Samples were degassed
between each cycle at 673 K.
of activation (hydrogenation at 3 MPa at 303 K followed by the
degassing of materials at 673 K). This activation procedure
is shorter than the previously presented for arc melted
Ti1.0V1.1Mn0.9 alloy for which two cycles of activation were
needed (initial hydrogenation at 5 MPa of hydrogen gas,
evacuation at 353 K for 1h) [31]. The activation procedure of
TieVeMn alloys, described by T. Bibienne et al., also seems to
be more complicated than the one used in this work [32].
All of the studied samples can absorb hydrogen without
any incubation time when they are activated. The initial
phase of the hydrogenation process is very fast. The time
needed to saturate studied V-rich alloys does not depend on
the chemical composition of a material. It lasts 60e67 min for
15523
all of the alloys. However, most of the hydrogen is absorbed
during the first 10 min of a process.
PeC isotherms received for studied V-rich alloys at 303 K
are presented in Fig. 2. On these curves one plateau region,
characterized by a large slope is visible. The equilibrium
plateau slope is undesirable for the application of metal hy-
drides. As C.Y. Seo et al. wrote, Mn is considered as an effec-
tive element in decreasing the slope of the plateau pressure
[22]. However, an opposite tendency has been observed in
this work - the slope enhances with Increasing Mn content in
BCC alloys. To make the plateau region flatter, materials can
be homogenized by the heat treatment [33].
The equilibrium pressure and the width of plateau depend
on a chemical composition of BCC alloys. The increase of Mn
content results in narrowing of the plateau, increasing of
the equilibrium pressure and decreasing of the hydrogen
sorption/desorption hysteresis. The increase of the plateau
pressure causes less hydride stability which results in easier
hydrogen desorption.
It is well known from the literature that the absorption of
hydrogen in BCC alloys occurs through three steps [11,34]:
- firstly, when the hydrogen is applied, a BCC-based solid
solution hydride phase is formed (hydrogen atoms
randomly occupy octahedral interstitial sites of BCC metal
lattice). The maximum hydrogen capacity of this solid so-
lution reaches 1.5 wt%. Hydrogen desorption is impossible
in ambient conditions from this hydride.
- while the hydrogen pressure increases, hydrogen atoms
start to occupy octahedral sites in ordered way, creating
monohydride phase with the body-centered-tetragonal
(BCT) structure (I4/mmm space group). This phase corre-
sponds to BCC structure elongated along c axis. The
maximum hydrogen uptake of BCT phase is 1.9 wt%,
- finally, further increase of the hydrogen pressure causes
filling of tetrahedral interstitial sites and formation of
the dihydride phase characterized by the face-centered-
cubic (FCC) structure (Fm-3m space group). The
maximum hydrogen uptake of FCC phase is 4 wt%. It is
noteworthy that Ti and V metals are known to form a
hydride with FCC structure and Mn is a hydride non-
forming element [31].
Fig. 2 e PeC Isotherms at 303 K of Ti0.5V1.5-xMnx alloys
(obtained on degassed samples).
15524 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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9
The plateau region that is visible on PeC isotherms corre-
sponds most likely to a two-phase region of the hydrogenated
solid-solution phase (distorted BCC) and BCT hydride phase.
Moreover, it is noteworthy that there may be another plateau
region related to an irreversible hydrogen storage. This region
can occur below the current PCT measuring range [19].
When the Mn content increases in TieVeMn alloys, the
maximum hydrogen storage capacity at room temperature
firstly increases to 3.07 wt% for Ti0.5V1.4Mn0.1 alloy and then
gradually decreases to reach 1.81 wt% for Ti0.5V1.2Mn0.3
alloy. Maximum hydrogen storage capacities of studied
Ti0.5V1.5-xMnx alloys are much higher than those obtained for
the arc melted TieVeMn Laves phase related BCC alloys.
Based on the available data presented in the literature, the
unambiguous indication of the reason for this difference is
impossible. This may be due to different chemical composi-
tion, phase composition, microstructure etc. [22,23,35].
A hydrogen desorption properties of tested V-rich alloys
are quantitatively represented by a reversibility of hydriding-
dehydriding process. Only 11% of hydrogen absorbed in
Ti0.5V1.5 alloy can be easily desorbed in ambient conditions.
The reversibility has been improved by the chemical modifi-
cation of studied alloys by Mn atoms and reaches 28% for
Ti0.5V1.3Mn0.2 and Ti0.5V1.2Mn0.3 alloys.
Microstructural, structural and thermal studies
Time-capacity curves that have been presented in Fig. 1
have shown that activated MA V-rich alloys absorb
hydrogen without incubation time. These results differ much
from those obtained by X.B Yu et al. This group reported that
TieVeMneCr alloy that was synthesized by a magnetic
levitation melting method needs 10e30 min (depending on
melt-quenching time) to start the hydrogen sorption process
[36]. The reason for the different performance of studied
and referenced materials can originate from their different
microstructures. The grain size of melted samples is sub-
micrometric [36]. Fig. 3 presents HRTEM images of
Ti0.5V1.4Mn0.1 and Ti0.5V1.2Mn0.3 alloys e which represent the
structure of all investigated BCC alloys. BCC materials do not
Fig. 3 e HRTEM images of a) Ti0.5V1.4Mn0.1 and b) Ti0.5V1.2Mn0.3 alloys.
Table 2 e Average particle size, crystallites size and
lattice strain of obtained alloys.
Sample Average particle Crystallites Lattice
size (mm) size (nm) strain (%)
Ti0.5V1.5 14.6 5.4 1.1
Ti0.5V1.4Mn0.1 18.0 3.8 2.0
Ti0.5V1.3Mn0.2 7.4 3.2 2.4
Ti0.5V1.2Mn0.3 4.5 5.6 1.4
differ in the microstructure. TieVeMn alloys are character-
ized by a multicrystalline structure e nanocrystals with
different orientations, form a more complex structures. The
size of crystallites (clearly visible on HRTEM images) varies
between a few and 10 nm. It is noteworthy that nanocrystal-
line materials are characterized by large number of grain
boundaries. Hydrogen can diffuse on the grain boundaries
more easily than in the bulk region. Therefore, the hydrogen
diffusion path is shorter in nanocrystalline than in micro-
crystalline or submicrocrystalline materials. Thus the incu-
bation time and kinetic properties are better in presented
nanocrystalline alloys.
Further microstructure studies were made using SEM.
Fig. S1 shows SEM micrographs (secondary electron images) of
Ti0.5V1.5-xMnx alloys. Synthesized alloys are made of irregular
particles which are characterized by porous, cleavage and
fracture morphology. Alloys particles size distribution shows
bimodal character e small grains (size of a few mm) are
agglomerated in much bigger forms (from tens to hundred
mm).
Particle size dimension distribution histograms for
Ti0.5V1.5-xMnx alloys were made based on SEM micrographs
(insets of Fig. S1). Moreover, in Table 2 the average particle size
of V-rich alloys is presented. It is easy to see that the partial
substitution of V by Mn atoms firstly results in an increase of
average particle size - from 14.6 mm for Ti0.5V1.5e18.0 mm for
Ti0.5V1.4Mn0.1. For alloys with Mn content higher than x ¼ 0.1 a
reduction of particle sizes has been observed e the average
value reaches 4.5 mm for Ti0.5V1.2Mn0.3. Smaller particle size
effects on higher specific surface area which can result in
 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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9 15525

faster hydrogenation kinetics and easier access of hydrogen to

the bulk. However, such an effect has not been observed in
this work.
Gradual decrease of hydrogen storage capacity visible in
Fig. 2 for Ti0.5V1.3Mn0.2 and Ti0.5V1.2Mn0.3 alloys could be
caused by an inhomogeneity of the materials chemical
composition. A part of material could be composed of a sec-
ondary phase that does not absorb hydrogen (for example Mn
a-phase). The effective mass of the hydrogen absorbing ma-
terial could be reduced causing the reduction of hydrogen
storage capacity. However, EDS mappings of Ti0.5V1.2Mn0.3
alloy (Fig. 4) showed that all elements are homogeneously
distributed throughout the V-rich alloy. No local concentra-
tion of Ti, V or Mn has been observed.
Hydrogen storage properties often result from the struc-
ture of material. XRD patterns of Ti0.5V1.5-xMnx alloys ball
milled for 14h are shown in Fig. 5. All of the studied alloys
are composed of main BCC structure (Im-3m space group).
Moreover, in modified TieVeMn alloys, a minor phase char- Fig. 5 e XRD patterns of MA Ti0.5V1.5-xMnx alloys. Inset
acterized by the same BCC structure has been detected. The corresponds to part of XRD patterns surrounded by dashed
lattice parameter of minor phase is smaller than of the main lines.
phase. The coexistence of two BCC phases is clearly visible in
an inset of Fig. 5 where (110) peaks of both phases are over-
lapped. The structure of main phase of TieVeMn alloys has conclusion, the only two detected phases are BCC structures
been also confirmed by fast Fourier transformation (FFT) of which are able to absorb hydrogen in appropriate conditions.
the HRTEM image (Fig. S2). Moreover, it is noteworthy that Mn According to the presented above results of kinetic mea-
which crystalizes in BCC structure in room temperature surements, it is noteworthy that S.F. Santos et al., who studied
(I-43 m space group) has not been detected on XRD patterns. It TieMn-(FeV) Laves phase related BCC alloys stated that the
means that the Mn-based solid solution is not created and Mn presence of incubation time in BCC alloys could be related to
can be easily incorporated into TieV-based BCC phase [37]. In the absence of C14 Laves phase [28]. However, materials

Fig. 4 e SEM micrograph of Ti0.5V1.2Mn0.3 (a), corresponding EDS elements maps of Ti Ka (b), V Ka (c), Mn Ka (d).
15526 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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9

which have been studied in this paper are not composed of

C14 Laves phase and the incubation time has not been
observed. Therefore, the presence of C14 Laves phase is not
crucial for the elimination of incubation time problem from
BCC hydrogen storage alloys.
The weight fractions of BCC phases in Ti0.5V1.5-xMnx alloys
have been obtained by the Rietveld refinement of XRD data.
The abundance of minor BCC phase increases with the in-
crease of Mn content to reach 41.62 wt% for Ti0.5V1.2Mn0.3 alloy
(Table 3). For example, Fig. S3 shows the results of the Rietveld
refinement made on Ti0.5V1.2Mn0.3 alloy, in which Rwp is 5.91 Fig. 6 e Lattice parameter as a function of x in
and S is 1.29. It is noteworthy that the d100 spacing value Ti0.5V1.5-xMnx alloys (black squares refer to BCC main
phase, red dots refer to BCC minor phase). (For
(0.217 nm) obtained from the Rietveld refinement of
Ti0.5V1.4Mn0.1 XRD data is similar to that presented in HRTEM interpretation of the references to colour in this figure
micrograph (Fig. 3). legend, the reader is referred to the Web version of this
Since V and Mn elements have different atomic sizes, the article.)
chemical composition is considered to affect the alloys lattice
parameters. As expected, peaks positions (corresponding to
both BCC phases) are shifted toward higher angles while Mn improvement mechanism. Therefore, the additional electronic
element content in studied Ti0.5V1.5-xMnx alloys increases. structure measurements need to be performed.
This implies the decrease of the unit cell volume. When x in Ti0.5V1.5-xMnx alloys exceeds 0.1 the hydrogen
Fig. 6 shows a variation of lattice parameters of storage capacity decreases gradually to reach 1.81 wt% for
Ti0.5V1.5-xMnx alloys with an increase of substitution, which Ti0.5V1.2Mn0.3 alloy. One of its explanations is that the amount of
clearly shows the effect of chemical modification on lattice the main BCC phase which works as the main hydrogen storage
parameters. Lattice parameters were obtained from the Riet- medium is decreased and thus, the hydrogen storage capacity is
veld refinement method (Table 3). The lattice parameter also decreased. However, the secondary phase can also react
decreased linearly with increasing Mn in Mn-containing al- reversibly with hydrogen. Therefore, the increase in the
loys. This is related to an atomic size effect: the Goldschmidt amount of secondary phase cannot be taken as sole reason for
radii for V and Mn are 0.135 and 0.112(a)~0.137(g) nm, the decrease in the maximum hydrogen desorption capacity.
respectively [38]. The same tendency was noticed for Laves For this reason, the decrease in maximum hydrogen storage
phase related BCC alloys for which lattice parameters of both capacity is most likely related to the increase of plateau equi-
phases (BCC and Laves) decreased with increasing Mn content librium pressure which is caused by the reduction of the
[15]. As can be seen from Fig. 6, the lattice parameter of the hydrogen stability due to the decrease of the lattice parameters.
main phase decreases more than that of the minor phase. It XRD data was used to determine an average crystallite size
means that introduced Mn atoms dissolve slightly more in the and a lattice strain (Table 2). There is no tendency of the
main BCC phase than in the minor BCC phase. crystallite size and the lattice strain changes with the
As PCT-curves obtained for TieVeMn alloys showed (Fig. 2), increasing Mn concentration in the alloy. Crystallite sizes
the maximum hydrogen capacity firstly increases to reach obtained from Williamson-Hall style plot are in the same
3.07 wt% for Ti0.5V1.4Mn0.1 alloy. The increase of initial capacity range of magnitude as those which can be seen on HRTEM
results from the catalytic function of Mn and Mn content in image (Fig. 3).
BCC alloy. However, based on the presented structural and Activated and fully hydrogenated Ti0.5V1.5-xMnx alloys
microstructural data, it is impossible to describe the capacity were studied by XRD and DSC. XRD patterns of studied BCC
alloys in the hydrogenated state are presented in Fig. 7. All of
the hydrides are composed of two phases: distorted BCC
Table 3 e Structural parameters obtained from the phase (a-phase) and BCT phase. The coexistence of two pha-
Rietveld refinement of TieVeMn X-ray diffraction data. ses is clearly visible in the inset of Fig. 7 where the most
intensive peaks of both phases are overlapped. The coexis-
Sample Phase a (
A) V (
A3) Pabund (wt.%)
tence of these two hydride phases in Ti0.5V1.5-xMnx alloy was
Ti0.5V1.5 BCC 3.1066 29.9817 100
also proved and analysed by Rietveld refinement method. For
Rwp ¼ 4.11
example, the results of XRD Ti0.5V1.5 data analysis are shown
S ¼ 1.17
Ti0.5V1.4Mn0.1 BCC 3.0843 29.3407 95.12 in Fig. S4. The BCT phase abundance decreased with the in-
Rwp ¼ 8.08 BCC 3.0469 28.2862 4.88 crease of Mn in studied BCC alloys e from 32.3% for unmodi-
S ¼ 1.48 fied Ti0.5V1.5e4.4% for Ti0.5V1.2Mn0.3 alloy. The reduction of
Ti0.5V1.3Mn0.2 BCC 3.0795 29.2039 84.23 BCT phase concentration fits well to the reduction of hydrogen
Rwp ¼ 6.05 BCC 3.0421 28.1527 15.77 storage capacities observed for TieVeMn alloys. However, it
S ¼ 1.21
does not explain the initial increase of the capacity observed
Ti0.5V1.2Mn0.3 BCC 3.0693 28.9147 58.38
for Ti0.5V1.4Mn0.1 alloy.
Rwp ¼ 5.91 BCC 3.0373 28.0197 41.62
S ¼ 1.29 It is noteworthy that the hydrogen concentration obtained
for Ti0.5V1.5 and Ti0.5V1.4Mn0.1 alloys greatly exceeds the
Pabund - phase abundance.
maximum hydrogen capacity of BCT phase (up to 1.9 wt%). It
 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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9
Fig. 7 e XRD patterns of fully hydrogenated Ti0.5V1.5-xMnx
alloys. Inset corresponds to part of XRD patterns
surrounded by dashed lines.
was shown in the previous work that the Ti0.5V1.5 alloy is
partially composed of FCC phase [15]. This phase has not been
detected during the Rietveld refinement due to its low content.
Fig. 8 shows DSC profiles obtained on fully hydrogenated
Ti0.5V1.5 and Ti0.5V1.2Mn0.3 alloys (heating rate of 10 K/min, an
argon atmosphere). As has been discussed previously, the DSC
profile of Ti0.5V1.5 alloy consists of three endothermic peaks
related to three phase transformations in the regions
532e551K, 631e638K and 716e744K, respectively. The first,
low-temperature hydride decomposition reaction is associ-
ated with the phase transformation from FCC to BCT phase. In
the next step, the BCT decomposes to hydrogenated BCC
phase. At last, the high-temperature peak is associated with
the decomposition of hydrogenated BCC phase to dehydro-
genated BCC phase.
DSC profile which has been obtained for Ti0.5V1.2Mn0.3 alloy
contains only two endothermic peaks which correspond to BCT-
hydrogenated BCC and hydrogenated BCC-dehydrogenated BCC
phase transitions. The FCC hydride phase has not been created
during hydrogenation of Ti0.5V1.2Mn0.3 which fits well to PCT
studies results. The BCC dehydrogenation temperature is
Fig. 8 e DSC profiles of Ti0.5V1.5 and Ti0.5V1.2Mn0.3 alloys
(endothermic downwards).
15527
slightly decreased after the chemical modification of TieV alloy.
The temperature of the peak decreases from 723.5 K to 713.2 K.
The enthalpy of this dehydrogenation process reached 240.3 and
132.7 J/g respectively for x ¼ 0 and 0.3. It implies that the addition
of Mn can be effective in reducing of the hydride stability.
The desorption temperatures that have been obtained
in this DSC measurements are not the exact one, due to air
poisoning of alloys during transferring of BCC powder from
the glove box to DSC device. However, the stability of hy-
drides phases can be compared quite well. Unfortunately,
the dehydrogenation temperatures are high. These results
indicate the high thermal stability of hydride phases.
The hydride decomposition temperature needs to be low-
ered in order to consider BCC alloys as hydrogen storage
systems.
Conclusions
Based on studies of hydrogenation/dehydrogenation, struc-
ture, microstructure and hydrides thermal properties of BCC
alloys, the effect of Mn content on hydrogen storage proper-
ties of nanocrystalline Ti0.5V1.5-xMnx has been investigated in
present work. The obtained results can be summarized as
follows:
- Ti0.5V1.5-xMnx alloys can be easily activated and can absorb
hydrogen without any incubation time due to their nano-
crystalline microstructure,
- hydrogenation/dehydrogenation properties of BCC alloys
are related to the chemical composition and the lattice
parameters. When the Mn content in TieVeMn alloys in-
creases, the maximum hydrogen storage capacity at room
temperature firstly increases to 3.07 wt% for Ti0.5V1.4Mn0.1
alloy and then gradually decreases to reach 1.81 wt% for
Ti0.5V1.2Mn0.3 alloy. The origin of the initial capacity in-
crease is not clear and additional electric structure need to
be done. The reason of capacity decrease that occurs for
Ti0.5V1.3Mn0.2 and Ti0.5V1.2Mn0.3 alloys is a reduction of cell
volumes of BCC phases,
- the chemical modification by Mn atoms improves the
reversibility of hydriding/dehydriding process,
- the partial substitution of V by Mn atoms results in the
creation of minor BCC phase. Its abundance increases with
increase of Mn content in the alloy,
- MA method provides a synthesis of TieVeMn alloys with a
chemical composition that is close to expected.
Acknowledgements
Financial assistance from National Science Centre, Poland (no.
2015/17/N/ST8/00271).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2019.02.092.
15528 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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9

references Alloy Comp 2005;386:258e60. https://doi.org/10.1016/

j.jallcom.2004.05.014.
[17] Young K, Ouchi T, Nei J, Meng T. Effects of Cr, Zr, V, Mn, Fe,
and Co to the hydride properties of Laves phase-related
[1] Ouyang L, Cao Z, Wang H, Hu R, Zhu M. Application of
body-centered-cubic solid solution alloys. J Power Sources
dielectric barrier discharge plasma-assisted milling in energy
2015;281:164e72. https://doi.org/10.1016/
storage materials e a review. J Alloy Comp 2017;691:422e35.
j.jpowsour.2015.01.170.
https://doi.org/10.1016/j.jallcom.2016.08.179.
[18] Huot J, Enoki H, Akiba E. Synthesis, phase transformation,
[2] Cao Z, Ouyang L, Wang H, Liu J, Sun L, Zhu M. Composition
and hydrogen storage properties of ball-milled TiV0.9Mn1.1. J
design of Ti-Cr-Mn-Fe alloys for hybrid high-pressure metal
Alloy Comp 2008;453:203e9. https://doi.org/10.1016/
hydride tanks. J Alloy Comp 2015;639:452e7. https://doi.org/
j.jallcom.2006.11.193.
10.1016/j.jallcom.2015.03.196.
[19] Yoo JH, Shim G, Park CN, Kim WB, Cho SW. Influence of Mn
[3] Cao Z, Ouyang L, Wang H, Liu J, Sun L, Felderhoff M, et al.
or Mn plus Fe on the hydrogen storage properties of the Ti-
Development of Zr-FeV alloys for hybrid hydrogen storage
Cr-V alloy. Int J Hydrog Energy 2009;34:9116e21. https://
system. Int J Hydrog Energy 2016;41:11242e53. https://
doi.org/10.1016/j.ijhydene.2009.08.064.
doi.org/10.1016/j.ijhydene.2016.04.083.
[20] Pickering L, Li J, Reed D, Bevan AI, Book D. Ti-V-Mn based
[4] Cao Z, Ouyang L, Wang H, Liu J, Sun D, Zhang Q, et al.
metal hydrides for hydrogen storage. J Alloy Comp
Advanced high-pressure metal hydride fabricated via Ti-Cr-
2013;580:S233e7. https://doi.org/10.1016/
Mn alloys for hybrid tank. Int J Hydrog Energy
j.jallcom.2013.03.208.
2015;40:2717e28. https://doi.org/10.1016/
[21] Shibuya M, Nakamura J, Akiba E. Hydrogenation properties
j.ijhydene.2014.12.093.
and microstructure of Ti-Mn-based alloys for hybrid
[5] Yu XB, Feng SL, Wu Z, Xia BJ, Xu NX. Hydrogen storage
hydrogen storage vessel. J Alloy Comp 2008;466:558e62.
performance of Ti-V-based BCC phase alloys with various Fe
https://doi.org/10.1016/j.jallcom.2007.11.120.
content. J Alloy Comp 2005;393:129e34. https://doi.org/
[22] Seo CY, Kim JH, Lee PS, Lee JY. Hydrogen storage properties
10.1016/j.jallcom.2004.09.058.
of vanadium-based b.c.c. solid solution metal hydrides. J
[6] Yu XB, Wu Z, Xia BJ, Xu NX. Enhancement of hydrogen
Alloy Comp 2003;348:252e7. https://doi.org/10.1016/S0925-
storage capacity of Ti-V-Cr-Mn BCC phase alloys. J Alloy
8388(02)00831-9.
Comp 2004;372:272e7. https://doi.org/10.1016/
[23] Nakamura Y, Akiba E. Hydriding properties and crystal
j.jallcom.2003.09.153.
structure of NaCl-type mono-hydrides formed from Ti-V-Mn
[7] Kim H, Sakaki K, Nakamura Y. Improving the cyclic stability
BCC solid solutions. J Alloy Comp 2002;345:175e82. https://
of V-Ti-Mn bcc alloys using interstitial elements. Mater
doi.org/10.1016/S0925-8388(02)00434-6.
Trans 2014;55:1144e8. https://doi.org/10.2320/
[24] Challet S, Latroche M, Heurtaux F. Hydrogenation properties
matertrans.MG201412.
and crystal structure of the single BCC (Ti0.355V0.645)100-xMx alloys
[8] Aoki M, Noritake T, Ito A, Ishikiriyama M, Towata S.
with M ¼ Mn, Fe, o, Ni (x ¼ 7, 14 and 21). J Alloy Comp
Improvement of cyclic durability of Ti-Cr-V alloy by Fe
2007;439:294e301. https://doi.org/10.1016/j.jallcom.2006.08.070.
substitution. Int J Hydrog Energy 2011;36:12329e32. https://
[25] Mouri T, Iba H. Hydrogen-absorbing alloys with a large capacity
doi.org/10.1016/j.ijhydene.2011.07.019.
for a new energy carrier. Mater Sci Eng 2002;A329e331:346e50.
[9] Wu C, Zheng X, Chen Y, Tao M, Tong G, Zhou J. Hydrogen
https://doi.org/10.1016/S0921-5093(01)01597-0.
storage and cyclic properties of V60Ti(21.4þx)Cr(6.6-x)Fe12 (0  x
[26] Chen XY, Chen RR, Ding X, Li XZ, Ding HS, Su YQ, et al.
 3) alloys. Int J Hydrog Energy 2010;35:8130e5. https://
Substitution effect of Hf on hydrogen storage capacity and
doi.org/10.1016/j.ijhydene.2010.01.017.
cycling durability of Ti23V40Mn37 metal hydride alloys. Int J
[10] Huang Z, Cuevas F, Liu X, Jiang L, Wang S, Latroche M, et al.
Hydrog Energy 2018;43:19567e74. https://doi.org/10.1016/
Effects of Si addition on the microstructure and the hydrogen
j.ijhydene.2018.08.203.
storage properties of Ti26.5V45Fe8.5Cr20Ce0.5 BCC solid solution
[27] Chen XY, Chen RR, Ding X, Fang HZ, Guo JJ, Ding HS, et al.
alloys. Int J Hydrog Energy 2009;34:9385e92. https://doi.org/
Crystal structure and hydrogen storage properties of Ti-V-
10.1016/j.ijhydene.2009.09.055.
Mn alloys. Int J Hydrog Energy 2018;43:6210e8. https://
[11] Couillaud S, Enoki H, Amira S, Bobet JL, Akiba E, Huot J. Effect
doi.org/10.1016/j.ijhydene.2018.02.009.
of ball milling and cold rolling on hydrogen storage
[28] Santos SF, Huot J. Hydrogenation storage in Ti-Mn-(FeV) BCC
properties of nanocrystalline TiV1.6Mn0.4 alloy. J Alloy Comp
alloy. J Alloy Comp 2009;480:5e8. https://doi.org/10.1016/
2009;484:154e8. https://doi.org/10.1016/j.jallcom.2009.05.037.
j.jallcom.2008.09.191.
[12] Kumar A, Shashikala K, Banerjee S, Nuwad J, Das P,
[29] Yu XB, Wu Z, Xia BJ, Xu NX. The activation mechanism of Ti-
Pillai CGS. Effect of cycling on hydrogen storage properties of
V-based hydrogen storage alloys. J Alloy Comp
Ti2CrV alloy. Int J Hydrog Energy 2012;37:3677e82. https://
2004;375:221e3. https://doi.org/10.1016/j.jallcom.2003.11.027.
doi.org/10.1016/j.ijhydene.2011.04.135.
[30] Nakamura Y, Akika E. New hydride phase with a deformed
[13] Zhou HY, Wang F, Wang J, Wang ZM, Yao QR, Deng JQ, et al.
FCC structure in the Ti-V-Mn solid solution-hydrogen
Hydrogen storage properties and thermal stability of
system. J Alloy Comp 2000;311:317e21. https://doi.org/
V35Ti20Cr45 alloy by heat treatment. Int J Hydrog Energy
10.1016/S0925-8388(00)01148-8.
2014;39:14887e95. https://doi.org/10.1016/
[31] Yu XB, Wu Z, Xu NX. Effect of melt-quenching rates on the
j.ijhydene.2014.07.054.
hydrogen storage properties of Ti-based BCC alloy. Physica B
[14] Zhang QA, Lei YQ, Yang XG, Du YL, Wang QD. Influence of
2004;344:456e61. https://doi.org/10.1016/j.physb.2003.11.002.
Mn on phase structure and electrochemical properties of
[32] Bibienne T, Tousignant M, Bobet J-L, Hout J. Synthesis and
V3TiNi0.56Hf0.24 alloy. Int J Hydrog Energy 2000;25:657e61.
hydrogen sorption properties of TiV(2-x)Mnx BCC alloys. J
https://doi.org/10.1016/S0360-3199(99)00083-X.
Alloy Comp 2015;624:247e50. https://doi.org/10.1016/
[15] Balcerzak M. Structure and hydrogen storage properties of
j.jallcom.2014.11.060.
mechanically alloyed Ti-V alloys. Int J Hydrog Energy
[33] Yu XB, Wu Z, Xu NX. Effect of melt-quenching rates on the
2017;42:23698e707. https://doi.org/10.1016/
hydrogen storage properties of Ti-based BCC phase alloy.
j.ijhydene.2017.03.224.
Physica B 2004;344:456e61. https://doi.org/10.1016/
[16] Yu XB, Wu Z, Xia BJ, Xu NX. Improvement of activation
j.physb.2003.11.002.
performance of the quenched Ti-V-based BCC phase alloys. J
 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 5 ( 2 0 2 0 ) 1 5 5 2 1 e1 5 5 2 9
[34] Nakamura Y, Oikawa K, Kamiyama T, Akiba E. Crystal
structure of two hydrides formed from a Ti-V-Mn BCC solid
solution alloy studied by time-of-flight neutron powder
diffraction e a NaCl structure and CaF2 structure. J Alloy
Comp 2001;316:284e9. https://doi.org/10.1016/S0925-8388(00)
01503-6.
[35] Shibuya M, Nakamura J, Enoki H, Akiba E. High-pressure
hydrogenation properties of Ti-V-Mn alloy for hybrid
hydrogen storage vessel. J Alloy Comp 2009;475:543e5.
https://doi.org/10.1016/j.jallcom.2008.07.121.
[36] Lotoskyy MV, Yartys VA, Pollet BG, Bowman Jr RC. Metal
hydride hydrogen compressors: a review. Int J Hydrog Energy
15529
2014;39:5818e51. https://doi.org/10.1016/
j.ijhydene.2014.01.158.
[37] Young K, Nei J, Wong DF, Wang L. Structural, hydrogen
storage, and electrochemical properties of Laves phase-
related body-centered-cubic solid solution metal hydride
alloys. Int J Hydrog Energy 2014;39:21489e99. https://doi.org/
10.1016/j.ijhydene.2014.01.134.
[38] Inoue H, Kotani N, Chiku M, Higuchi E. Ti-V-Cr-Ni alloys as
high capacity negative electrode active materials for use in
nickel-metal hydride batteries. Int J Hydrog Energy
2016;41:9939e47. https://doi.org/10.1016/
j.ijhydene.2016.02.004.