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1 s2.0 S0360319919306767 Main
1 s2.0 S0360319919306767 Main
ScienceDirect
M. Balcerzak*
Institute of Materials Science and Engineering, Poznan University of Technology, Jana Pawła II no 24, 61-138 Poznan,
Poland
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
* 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.
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moreover, suffer from the high price of V. The price of these However, the differences between these compositions are
alloys can be reduced by substitution of expensive V atoms by rather small and can be associated with the accuracy of EDS
cheaper Mn atoms. method.
Recently, the author has reported the hydrogen storage Hydrogen sorption/desorption behaviour of Ti0.5V1.5-xMnx
properties of TieV BCC alloy synthesized for the first time by alloys was characterized at near room temperature by kinetic/
mechanical alloying (MA) method. Obtained nanocrystalline activation curves and pressure-composition isotherms (PCI) -
MA BCC alloys have shown good activation properties and fast measured by a Sieverts-type device (a product of Particulate
hydrogen sorption [15]. Ball milling was also used in the past Systems). The initial hydrogen pressure and temperature in
to produce the composite material based on microcrystalline kinetic/activation measurements equalled 3 MPa and 303 K,
TieVeMneCr BCC and LaNi5-type alloys. The synthesized respectively. These time-composition curves were obtained
material was characterized by improved activation perfor- using time-pressure curves and calculated hydrogen concen-
mance which resulted from created core-shell structure [17]. tration. The curves were normalized by assuming that the
Moreover, S. Couillaud et al. and J. Huot et al. used the ball hydrogen concentration: equals 0 wt% in t ¼ 0; reaches
milling in order to improve hydrogenation properties of arc maximum value in an equilibrium state. Details concerning
melted TieVeMn alloy [11,19]. these studies were included in the previous work [15].
However, to the best of author' knowledge, there is no in- Structural, microstructural and thermal analyses were
formation concerning on nanocrystalline TieVeMn BCC alloys performed to explain the changes in hydrogen storage prop-
synthesized by MA method. Moreover, in the past, TieVeMn- erties of TieVeMn alloys. The microstructure was examined by
type alloys were studied as Laves phase related BCC alloys and scanning electron microscopy (SEM) e Tescan VEGA TS5135.
there is no information on the structural and hydrogen storage Micrographs were used to make particle size dimension dis-
properties of simple TieVeMn BCC alloys [6,14,15,18e28]. For tribution histograms. High resolution transmission electron
this reason, this work is focused on studies of hydrogenation microscope (HRTEM) e Joel ARM 200 F was used to observe the
properties of MA Ti0.5V1.5-xMnx alloys (x ¼ 0, 0.1, 0.2, 0.3). The microstructure in details. The crystal structure and lattice pa-
obtained results are discussed with reference to the current rameters of MA alloys were determined by X-ray powder
state of knowledge. 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
Experimental procedure refinement Maud program. Williamson-Hall style plot was
used to evaluate average crystallite size and lattice strain of MA
Samples of Ti0.5V1.5-xMnx alloys (x ¼ 0, 0.1, 0.2, 0.3) were pre- alloys. Differential scanning calorimetry (DSC) studies were
pared by MA the constituent metals under argon atmosphere made on fully hydrogenated samples under argon protective
(99.5% powder Ti, 99.5% powder V, 99.95% powder Mn). MA gas with a constant heating rate of 10K/min e TA DSC Q20.
lasted 14h to obtain BCC alloys. Details about MA process were It should be noticed, that studied Ti0.5V1.5-xMnx alloys and
included in the previous work [15]. Chemical compositions of additionally synthesized Ti0.5V1.4-xNi0.1Mnx alloys have been
obtained alloys were studied by energy dispersive X-ray also tested for their usefulness as negative electrodes in Ni-
spectrometer (EDS) e Tescan VEGA TS5135. The average MHx secondary electrodes. The electrochemical test results
elemental compositions of all studied BCC alloys are listed in are not shown in this work because increasing Mn content
Table 1. EDS data show that chemical compositions of ob- has not improved the electrochemical properties of TieV and
tained alloys are not matched to expected compositions. TieVeNi alloys. The same conclusion was also reported by
Q.A. Zhang et al. for the Laves phase related BCC alloys [15].
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).
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Conclusions
Acknowledgements
Fig. 8 e DSC profiles of Ti0.5V1.5 and Ti0.5V1.2Mn0.3 alloys Supplementary data to this article can be found online at
(endothermic downwards). https://doi.org/10.1016/j.ijhydene.2019.02.092.
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