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 1 6 3 2 e1 1 6 4 0

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Thermodynamic and microstructural basis for the

fast hydrogenation kinetics in MgeMg2Ni-carbon
hybrids

Anshul Gupta a, Mohammad Faisal b,*,1, Suboohi Shervani a,

Kantesh Balani a, Anandh Subramaniam a
a
Department of Materials Science and Engineering, Indian Institute of Technology, Kanpur 208016, India
b
Center for Energy Materials Research, Korea Institute of Science and Technology, Seoul 02792, Republic of Korea

highlights

The MgeMg2Ni-graphite hybrid shows enhanced capacity (5.9 wt%H at 260  C).

The improved capacity of the hybrid arises via storage of hydrogen in two phases.

The rate limiting step for hydrogen desorption is interface migration.

The reduced activation energy arises due to microstructural refinement via ARB.

article info abstract

Article history: Mg-based hybrids have shown promise via enhanced hydrogen storage properties. The Mg
Received 19 July 2019 eMg2Ni-carbon hybrid can be synthesized by accumulative roll bonding (ARB), which is
Received in revised form amenable to ‘scaled-up’ synthesis. In spite of the ‘bulk’ nature of the samples synthesized,
2 February 2020 they display fast kinetics of absorption and desorption of hydrogen. In the current work,
Accepted 7 February 2020 we try to comprehend the basis for the same in terms of the activation energy of the un-
Available online 6 March 2020 derlying processes involved; via desorption curves (wt.% H - time curves) in a Sievert’s
apparatus and differential scanning calorimetry (heat evolved - T plots). Analysis invoking
Keywords: the Johnson-Mehl-Avrami model and Kissinger plots show that the significantly reduced
Solid state hydrogen storage activation energy for the dehydrogenation process in the hybrid is responsible for the rapid
Hybrids kinetics. It is evinced that admixing the additives with Mg, coupled with fine scale
Pressure-composition-isotherms microstructure rich in interfaces is responsible for the fast kinetics. It is established that
Differential scanning calorimetry the rate limiting step for hydrogen desorption is interface migration and not the diffusion
of hydrogen, which is governed by the JMA-3D model.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author. Center for Energy Materials Research, Korea Institute of Science and Technology, Seoul, 02792, Republic of
Korea.
E-mail address: faisal@kist.re.kr (M. Faisal).
1
Co-first author.
https://doi.org/10.1016/j.ijhydene.2020.02.037
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 1 1 6 3 2 e1 1 6 4 0
Introduction
One of the major impediment in implementation of hydrogen
economy is the storage of hydrogen [1,2]. Solid state hydrogen
storage has been studied using plethora of materials viz. high
surface area materials such as CNTs and MOFs in which
hydrogen is adsorbed in molecular form and metals such as Pd
which store hydrogen in atomic form [3e5]. Important classes
of metallic systems for hydrogen storage include [6,7]: pure
metals (e.g. Mg, Pd, etc.), AB compounds (e.g. TiFe, ZrNi, etc.),
A2B compounds (e.g. Mg2Ni, Ti2Ni, etc.) and AB5 compounds
(e.g. LaNi5, CaNi5, etc.). Hybrids have shown considerable
promise for hydrogen storage in the solid state and hence
have been intensely investigated as alternatives to monolithic
materials [8,9]. The limits imposed on the use of monolithic
materials for hydrogen storage can be considerably enhanced
via microstructure engineering and the use of hybrids
[10].These limitations specifically relate to a preferred com-
binations of thermodynamic (temperature and pressure of
absorption and desorption) and kinetic parameters (rate of
absorption and desorption) [11]. Hybrids have been shown to
improve the hydrogen absorption and desorption properties,
which include [12]: enhanced storage capacity, faster kinetics
of absorption and lower temperature of absorption. Multiple
techniques have been used for the synthesis of hybrids, which
include accumulative roll bonding [13], ball milling [14] and
arc plasma evaporation [15].
Mg is one of the most attractive materials in the class of
pure metals for on-board applications [16e19]. It possess the
following advantages: (a) high hydrogen storage capacity
(7.6 wt%), (b) abundance in nature (2.3% of earth’s crust) and
(c) low cost (2e3 USD per Kg). However, it suffers from mul-
tiple lacunae [20]: (a) high desorption temperature (>350  C),
(b) sluggish kinetics and (c) sensitive to atmospheric oxygen.
Severe plastic deformation techniques such as high pressure
torsion [21,22], cold rolling [23,24] and ball milling [25e27]
have been employed to overcome these drawbacks. Edalati
et al. [21] have used high pressure torsion to synthesise a BCC
solid solution based alloy (MgNi4Pd) with an ability to absorb
0.8 wt%H at 25  C and 100 bar. El-Eskandarany et al. [23] have
performed cold rolling of Mg rods (up to 300 passes) followed
by Ni sputtering (on the Mg surface) to show enhanced
hydrogen storage properties of 6.1 wt% at 200  C and 0.2 bar.
Mg-based hybrids have also shown considerable promise as
they exploit the inherent storage capacity of Mg with
enhancement in kinetics [28e33]. Zaluska et al. [27] have
synthesized MgeMg2Ni composites by ball milling and
observed considerably reduced hydrogen desorption temper-
ature (280  C). Liu et al. [29] have ball milled MgH2 with Gra-
phene Nanosheet and they have shown 6.3 wt% hydrogen
absorption at 300  C in 80 min. Faisal et al. [30] have synthe-
sized MgeLaNi5-soot hybrid by accumulative roll bonding
(ARB) process (30 roll passes, 50% reduction per pass). They
showed that the hybrid absorbs 5 wt% H at 250  C at a pressure
of 0.33 MPa (4.5 wt% hydrogen at a plateau pressure of less
than 0.08 MPa). ARB technique not only helps in the formation
of hybrid, but also introduces large number of defects and
interfaces in the hybrid, which enhance the hydrogen storage
capacity of the material. Lu et al. [31] have reported 6.27 wt%
11633
hydrogen storage capacity at 673 K for MgeTi composites
prepared using ball milling. Majid et al. [32] prepared
MgeTiFe0.8Mn0.2eFeegraphite composites using ball milling
and observed a reduction in the hydrogen desorption tem-
perature by 165  C as compared to pure Mg (350  C) [34]. Zlotea
have synthesized Mg2CoH5 nanoparticles supported on
porous carbon using bottom up approach which exhibit
decrease in desorption temperature to 550 K with enhanced
kinetics [35].
Multiple kinetic models have been used to study the
hydrogen absorption and desorption kinetics of hydrogen
storage materials [36]. The absorption of hydrogen with the
metal (such as Pd) takes place in the following steps: (a)
physisorption of hydrogen molecule on the surface, (b)
dissociation of the hydrogen molecule and chemisorption of
hydrogen atoms on the surface, (c) diffusion of hydrogen
atoms and (e) nucleation and growth of hydride phase. The
release of hydrogen from the hydride phase begins with the
decomposition of hydride phase, nucleation of the metal
phase, followed by diffusion of hydrogen atoms to the surface
and recombination of hydrogen atoms to form molecule on
the surface. To determine the rate limiting step, several
mathematical models have been used such as ‘shrinking-core’
model [37], JMA model (based on nucleation and growth)
[38,39] and the ‘multi-step’ kinetic model [40]. Important
literature in this context pertains to the work of Tanniru et al.
[41] and Wang et al. [29], who have reported diffusion of
hydrogen (in the hydride phase) as the rate limiting step for
desorption of hydrogen from magnesium hydride. Tanniru
et al. [40] have also highlighted the difficulty in the nucleation
of hexagonally closed packed Mg phase in the tetragonal MgH2
matrix. This impediment slows down the desorption kinetics.
The following tasks are undertaken in the present work. (i)
Synthesise MgeMg2Ni-graphite hybrids using ARB. (ii) Deter-
mine hydrogen desorption temperature using differential
scanning calorimetry (DSC). (iv) Use the pressure-composition
isotherms (PCI) & kinetics curves (wt.% hydrogen vs. time) and
DSC data to compute the activation energy and the enthalpy
of the processes involved. (v) Use kinetic models to determine
the rate controlling step during hydrogen desorption. Addi-
tionally, Mg and MgeMg2Ni samples were synthesized by ARB,
which were used to obtain reference data for comparison. It is
important to note here that ARB process has been chosen here
over other plastic deformation processes (such as cold rolling
or forging) because it generates [13]: (i) increased density of
defects such as dislocations and grain boundaries, (ii) fine
scale microstructure (ultra fine grain size, additive phase
particle size and thickness of layers) and (iii) large interface
area. Moreover, it also allows for addition of large amount of
second phase particles.
Experimental methodology
MgeMg2Ni-graphite hybrids were synthesized by the ARB
process [42]. This sample has been labeled as sample-A. For
reference, MgeMg2Ni (sample-B) and Mg (sample-C) were also
prepared using identical processing parameters. PCI data were
obtained using standard Sievert’s apparatus supplied by the
AMC, USA. Details of the operation of the apparatus for PCI
11634 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 1 6 3 2 e1 1 6 4 0

and kinetics data can be found elsewhere [13]. PCI data were
(iii)
obtained in the pressure range of 0.1e4 bar at 250  C, 260  C, (i) Mg-Mg2Ni-graphite (sample-Ah)

Endothermic Up
(ii) Mg-Mg2Ni (sample-Bh)
270  C and 300  C. Kinetics (wt.%H vs. time) data were obtained
(iii) Mg (sample-Ch)
at 290  C, 330  C and 350  C under 20 bar pressure (absorption)
(i)
and 1 bar hydrogen pressure (desorption).

Heat Flow (a.u.)

The differential scanning calorimetry (DSC) measurements Scan Rate- 5°C/min
were carried out using Simultaneous Thermal Analyzer (Per- (ii)
kinElmer, STA 6000). The experiments were carried out with a
flow of pure nitrogen (99.99%) at 20 mL/min. Three tempera-
ture scans were employed at a rate of 5, 10 and 15  C/min. Prior
to DSC measurements, hydrogenation of the samples was
carried out at 300  C and 20 bar for 1 h. The samples obtained
at the end of hydrogenation were labeled with a suffix ‘h’ at
the end of their sample name (as sample-Ah, sample-Bh and T (°C)
sample-Ch). Kissinger plots ðlnH =T2p vs: 1 =RTp Þ were used to
200 250 300 350 400 450 500
determine the activation energy of the dehydrogenation re-
action. From the DSC curves obtained at different heating Fig. 2 e DSC desorption curves for three kinds of
rates, the activation energy (Ea) and the pre-exponential factor hydrogenated samples: (i) Mg (sample-Ch), (ii) MgeMg2Ni
(A) was computed using the Kissinger equation: (sample-Bh) and (iii) MgeMg2Ni-graphite (sample-Ah).
 
H Ea
ln ¼ þA (1)
T2p RTP
for: (a) sample-A and (b) sample-Ah. Partially desorbed sam-
where, ‘H’ is the heating rate ( C/min), Ea is the activation
ples were also studied using XRD. Three samples were used to
energy (J/mole), Tp the peak temperature ( C), ‘R’ the universal
study phases formed during hydrogen desorption (at 290  C
gas constant (8.314 J/K/mole) and ‘A’ is a dimensionless con-
and 1 bar pressure) from sample-Ah: (i) sample-Ahd1 (at the
stant. The peak onset and peak temperatures were deter-
end of 300 s), (ii) sample-Ahd2 (at the end of 700 s) and (iii)
mined using the tangent intersection method. The
sample-Ahd3 (at the end of 1500 s). JADE 2.0 was used to carry
implementation of this method was carried out using Pyris
out Rietveld refinement and determine the phase fraction.
software (version 10) provided by PerkinElmer.
Details of the refinement procedure is mentioned in the sup-
The X-Ray diffraction (XRD) measurements of samples plementary information.
were carried out using PANalytical Empyrean instrument. A To ascertain the rate controlling step during hydrogen
step size of 0.026 with a dwell time of 100 s per step was used
desorption reaction, the compliance with the following
to obtain the XRD data. XRD measurements were performed

Fig. 1 e XRD pattern obtained from sample-Ah. Inset shows the weight percentage of the phases present.
 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 1 6 3 2 e1 1 6 4 0 11635

Fig. 3 e (a) DSC curves from MgeMg2Ni-graphite (sample-Ah) obtained at the following scan rates: (i) 5  C/min, (ii) 10  C/min
and (iii) 15  C/min. (b) Kissinger plot obtained from the DSC curves.

models was tested using the desorption kinetics data (wt.%- The scanning electron microscopy (SEM) was performed
time plot) [43e45]: (i) Johnson-Mehl-Avrami (JMA) model, (ii) using the JEOL JSM 7100 F equipment equipped with the EDAX
core-shell model and (iii) contracting volume model. The de- Oxford Instruments analyzer. The back scattered electron
tails regarding these models and the methodology to obtain (BSE) micrograph was taken at accelerating voltage of 20 kV at
the rate determining step, is given in supplementary infor- an operational current of 400 pA, keeping the working dis-
mation. The activation energy for hydrogen desorption reac- tance fixed at 8 mm. The sample-Ahd1 was used for micro-
tion was calculated using Arrhenius equation: scopic study. To prevent further desorption of hydrogen, the
  sample was quenched in liquid nitrogen before removing
Q
k ðTÞ ¼ ko exp  (2) from sample holder. It was then mounted using cold setting
RT
resin and polished in the presence of oil to prevent oxidation.
where ko is the rate constant of the reaction and Q is the
overall activation energy for the reaction.
1.8
5 A P=1 bar 3D-JMA y = −0.000621x + 1.640176
1.6 R² = 0.996
T=290°C
1.4 Experimental Data
1.2
[−ln (1-α)]

4 Linear fit
1.0
0.8 (b)
3
wt.%H

0.6
B
0.4
t (s)
0 400 800 1200 1600 2000
2

1
C (a)
0
300 700 1500
0 200 400 600 800 1000 1200 1400 1600 1800 2000
t (s)

Fig. 5 e Hydrogen desorption data from sample-Ah at

Fig. 4 e (a) Pressure composition isotherms (desorption)
plots obtained from the sample-A at 250  C, 260  C, 270  C
and 300  C. (b) Van't Hoff plot used to calculate enthalpy
and entropy of hydrogen desorption.
290  C and 1 bar pressure. The same data fitted to 3D-JMA
model is shown in inset. The mathematical equation
governing the model and linear fit parameter (R2) have
been shown alongside. The points A, B and C represent the
time at which the desorbing sample was subjected to ex-
situ XRD measurements.
11636 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 1 6 3 2 e1 1 6 4 0
Fig. 6 e X-ray diffraction data acquired from: (a) sample-
Ahd1, (b) sample-Ahd2 and (c) sample-Ahd3. Phase
fractions calculated using Rietveld refinement are shown
in the inset.
Results and discussions
Fig. 1 shows XRD pattern obtained from sample-Ah. The
sample consists of 91 wt% MgH2 and 9 wt% Mg2NiH4. The XRD
pattern obtained from sample-A has been shown in supple-
mentary information for reference.
Fig. 7 e BSE micrograph for the sample-Ahd1. EDX line
scan is overlaid on the micrograph.
Fig. 2 (i) shows the DSC plot obtained from sample-Ah at a
scan rate of 5  C/min. The peak onset temperature and peak
temperature are 290  C and 334  C, respectively. Fig. 2 (ii)
shows DSC plot obtained from sample-Bh at the same scan
rate. It is seen that peak onset temperature and peak tem-
perature are 326  C and 394  C, respectively. Fig. 2 (iii) shows
DSC plot obtained from sample-Ch at the same scan rate. The
peak onset temperature and peak temperature are 405  C and
426  C, respectively. It is observed that the peak onset and
peak temperature decrease from sample-Ch to sample-Ah.
The formation of MgeMg2Ni-graphite hybrid using ARB pro-
cess (sample-Ah) leads to a lowered desorption peak tem-
perature (334  C), with respect to Mg (ARB processed, sample-
Ch) and MgeMg2Ni hybrid (sample-Bh). The role played by
graphite is noteworthy here, as it shows no hydrogen ab-
sorption (desorption) at these temperatures.
Fig. 3 shows DSC curves from the hydrogenated MgeMg2-
Ni-graphite (sample-Ah) at following scan rates: (i) 5  C/min,
(ii) 10  C/min and 15  C/min. The Kissinger plot, as obtained
from these three curves, is shown as an inset to the figure.
Plots for sample-Ch and sample-Bh are shown in the supple-
mentary information. The activation energy values, as deter-
mined from the Kissinger plots, for the sample-Ch, sample-Bh
and sample-Ah are: (a) 275.52 kJ/mol, (b) 189.58 kJ/mol and (c)
145.50 kJ/mol, respectively. The activation energy decreases
first on the addition of Mg2Ni. Further decrease in the activa-
tion energy, on the addition of graphite, is to be noted.
Fig. 4 (a) shows PCI desorption curves obtained from
MgeMg2Ni-graphite samples at 250  C, 260  C, 270  C and
300  C. The van’t Hoff plot obtained using the equilibrium
plateau pressure of desorption curves is shown in Fig. 4 (b).
The enthalpy and the entropy of dehydrogenation, as deter-
mined from the van’t Hoff plot, are 81.06 kJ/mol and 145.06 J/
mol K, respectively. Similar values have been reported for
dehydrogenation of magnesium hydride in the work of
Kalisvaart et al. [46]. It is seen from these observations that
desorption enthalpy remains unaltered by the presence of
multiple components in the hybrid. It is important to note that
 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 1 6 3 2 e1 1 6 4 0 11637

the plateau region in the desorption curves has a peculiar
feature of ‘dropping and rising’. This is related to insufficient
time provided for the equilibrium to be established during the
beginning and end of the desorption. Similar nature of the PCI
curves has also been reported for pure Mg [47] & Mg based
composites [48,49]. It is to be noted that desorption curve ob-
tained at 250  C shows incomplete desorption, with about
0.6 wt% hydrogen left as residual hydrogen in the sample. The
formation of MgeMg2Ni-carbon hybrid helps to bring down
the desorption temperature to 290  C (peak onset for sample-
Ah in Fig. 2) without sacrificing the hydrogen storage capacity
(~6.2 wt%H at 300  C as shown in Fig. 4 (a)).
Fig. 5 (a) shows hydrogen desorption kinetics plot (wt.% H
vs. time) of sample-Ah at 290  C and 1 bar hydrogen pressure.
The hybrid desorbs 5 wt% H in 30 min (1800s), which is 900%
faster than that reported by Tanniru et al. for Mg powders
covered with Ni (0.5 wt%H at 290  C in 30 min) [40]. Hydrogen
desorption data fitted to the 3D-JMA model is shown Fig. 5 (b).
The plots using other kinetic models are shown in supple-
mentary information. The curve with the best linear fit
(R2 ¼ 99.6%) is obtained using the 3D-JMA model. During the
desorption of hydrogen from hydrogenated MgeMg2Ni-
graphite hybrid (sample-Ah), Mg appears to nucleate within
the bulk of the hydride, with kinetics controlled by the three-
dimensional growth of Mg nuclei.
To identify the phases formed during desorption, X-ray
diffraction measurements were carried out (ex-situ) on the
sample-Ah at the end of: (a) 300 s (sample-Ahd1), (b) 700 s
(sample-Ahd2) and (c) 1500 s (sample-Ahd3) of hydrogen
desorption. These correspond to points A, B and C in Fig. 5 (a).
Fig. 6 (a) shows X-ray diffraction pattern acquired from the
sample-Ahd1. The pattern shows the presence of 7 wt%
Mg2Ni, 3 wt% Mg2NiH4 and 90 wt% MgH2. This indicates that
Mg2NiH4 starts desorbing prior to MgH2. As the desorption
proceeds, Mg nucleates near the Mg2Ni particles (shown in
Fig. 7). The amount of Mg phase grows as the desorption
proceeds. The fraction of phases at the end of 700 s of
hydrogen desorption (sample-Ahd2) is 50 wt% Mg, 40 wt%
MgH2 and 10 wt% Mg2Ni (shown in Fig. 6 (b)). No signature of
Mg2NiH4 phase is detected. Minor fraction of MgH2 phase
(0.6 wt%) remains at the end of the desorption process (1500s),
as shown in Fig. 6 (c) for sample-Ahd3. The role of Mg2Ni in the
process can be effectively visualised as ‘hydrogen pump’,
which desorbs prior to MgH2 and accelerates the desorption of
hydrogen from MgH2. These steps are schematically shown in
Fig. 8.
BSE micrograph from sample-Ahd1 is shown in Fig. 7.
The micrograph shows formation of Mg phase (lighter
region) at the interface of MgH2 and Mg2Ni. The presence
of Mg is confirmed by the EDX line scan overlaid on the
micrograph. This is evident from the rise in the Mg Ka
intensity on traversing from MgH2 to Mg along the line.
Also, MgH2 appears relatively dark as compared to Mg due
to higher average atomic number. It is seen that the
presence of Mg phase is observed in close proximity to the
Mg2Ni particles. This indicates that second phase particles
help the nucleation of Mg phase. This nucleation at in-
terfaces within the bulk is a key factor in enhancing the
desorption rate. The multitude of internal sites pre-
dominates over the case wherein the nucleation of Mg
occurs only at the surface of the particle (as observed by
Tanniru et al. [40]).
A schematic representing the desorption process from
hydrogenated MgeMg2Ni-carbon hybrid is shown in Fig. 8.

Carbon MgH2 Mg2NiH4

Mg-Mg2Ni-carbon hybrid (b)
(hydrogenated)

(a) Interface

(f) (c)

Mg2Ni Mg Mg2NiH4
MgH2
MgH2 Interface

(e) (d)

Mg2Ni Mg2NiH4

MgH2 Mg MgH2 Mg2Ni

Fig. 8 e A schematic of the dehydrogenation process in the hydrogenated MgeMg2Ni-carbon hybrid. (a) The hydrogenated
sample. (b) A zoomed-in view from a microscopic region, showing multiple interfaces along with the presence of secondary
phases (carbon and Mg2NiH4). (c) Region showing the Mg2NiH4 phase along an interface. (def) The formation of phases
during the hydrogen desorption process at the end of: 300 s, 700 s & 1500 s. The red circles represent the hydrogen atoms.
(For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
11638 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 1 6 3 2 e1 1 6 4 0
These results highlight the importance of the ‘micro-
structure engineering’ process involved in the synthesis of the
hybrid; wherein a large interfacial area and high defect den-
sities are created. These interfaces and defect centres serve as
preferred nucleation sites for the hydride phase during
hydrogen desorption.
Summary and conclusions
The MgeMg2Ni-graphite hybrid displays enhanced
hydrogen desorption capacity (5.9 wt%H at 260  C at
0.45 bar) along with fast desorption kinetics (5 wt%H in
30 min at 290  C and 1 bar). The sample was synthesized
using the accumulative roll bonding technique, which is
amenable to bulk scalable production. Differential Scanning
Calorimetry, X-ray diffraction, scanning electron micro-
scopy, Pressure Composition Isotherms and kinetics plots
are used to comprehend the enhanced hydrogenation/
dehydrogenation properties. The improved capacity of the
hybrid arises via storage of hydrogen in two phases
(Mg2NiH4 and MgH2), apart from the expected contributions
from defects and interfaces. The decomposition tempera-
ture of the hybrid is reduced with respect to that for Mg. It is
demonstrated that the reduced activation energy for
hydrogen desorption (145.50 kJ/mol) is responsible for the
fast kinetics, which arises due to microstructural refine-
ment achieved via ARB. It is established that the rate
limiting step for hydrogen desorption is interface migration
and not the diffusion of hydrogen, which is governed by the
JMA-3D model.
Acknowledgement
The authors would like to acknowledge Mrs. Samata Samal
(MSE, IIT Kanpur) for help with SEM operation and Mr. G P
Bajpai and Dr. Siva Kant Mishra (MSE, IIT Kanpur) for the help
with the XRD measurements. The authors thank Ms. Aparna
Tripathi for her inputs towards the improvement of the
manuscript. The financial assistance from Science and Engi-
neering Research Board, Department of Science and Tech-
nology (SERB-DST), India under Grant No. EMR/2016/004987 is
acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2020.02.037.
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