Journal of Alloys and Compounds 905 (2022) 164169

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Journal of Alloys and Compounds

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Construction of carbon covered Mg2NiH4 nanocrystalline for hydrogen

storage ]]
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⁎ ⁎
Xiong Lu a, Liuting Zhang a, , Jiaguang Zheng a, Xuebin Yu b,
a
School of Energy and Power, Jiangsu University of Science and Technology, Zhenjiang 212003, China
b
Department of Materials Science, Fudan University, Shanghai 200433, China

a r t i cl e i nfo a bstr ac t

Article history: Decreasing the desorption temperature and formation enthalpy are two key challenges for the practical
Received 15 December 2021 application of magnesium-based hydrogen storage materials. In this paper, different Mg2Ni samples were
Received in revised form 23 January 2022 successfully synthesized, and the corresponding hydrogen storage kinetic and thermodynamic behaviors
Accepted 7 February 2022
were investigated. The carbon-covered nanocrystalline Mg2Ni started to take up hydrogen at room tem­
Available online 10 February 2022
perature and released hydrogen at 180 °C. Meanwhile, the hydrogenated sample fully desorbed hydrogen at
250 °C within 10 min, and absorbed 2.1 wt% hydrogen in 1 h at 125 °C. The absorption and desorption
Keywords:
Hydrogen storage activation energy of carbon-covered nanocrystalline Mg2Ni was calculated to be 20.8 ± 1.2 kJ/mol and
Nanocrystalline Mg2Ni 34.1 ± 2.4 kJ/mol, which were 74% and 78% lower than that of MgH2, respectively. The dehydrogenation
Carbon covering enthalpy of the carbon-covered nanocrystalline Mg2NiH4 sample was also reduced from 89.9 ± 4.0 kJ/mol
Kinetics of MgH2 to 67.0 ± 0.5 kJ/mol. In addition, the cycling kinetics was maintained after ten cycles. Further
Thermodynamics analysis revealed that the remarkably improved hydrogen storage property of Mg2NiH4 originated from the
combining effect of the alloying, carbon covering, and nanocrystalline strategy.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction
Hydrogen energy, which has the advantages of high energy
density, environment benignity, and renewability, is considered as
one of the most promising alternative energy for future world. [1–5]
Nevertheless, storing hydrogen in a safe, easy, and cost-effective way
remains to be the bottleneck restricting the large-scale practical
application and commercialization of hydrogen energy. [5–11].
Given the limitations of high-pressure gaseous (350–700 bar at
room temperature) and cryogenic liquid storage (−253 °C) in cost
and safety, hydrogen stored in solid-state materials can commend­
ably meet the criteria of hydrogen economy. [2,12–16] In particular,
magnesium hydride (MgH2) shows great potential to be a solid-state
hydrogen storage material owing to its high gravimetric and volu­
metric hydrogen density (7.6 wt%, 110 g/L), low cost, and excellent
reversibility, [17–21] which satisfied the requirement of USDOE
(a hydrogen storage system with 4.5 wt% gravimetric and 30 g/L
volumetric capacity). [22] Unfortunately, the sluggish hydrogen ab/
desorption kinetics, high operation temperature, and high formation
⁎
Corresponding authors.
E-mail addresses: zhanglt89@just.edu.cn (L. Zhang),
yuxuebin@fudan.edu.cn (X. Yu).
enthalpy of MgH2 (−76 kJ/mol H2) stand in the way to its practical
application. [10,23–27] Hence, numerous effective strategies have
been utilized to enhance the kinetics property and weaken the
thermodynamics stability of MgH2 by reducing the particle size,
adding catalysts, surface modification, and alloying with metals (Ni,
Zn, Al, etc). [28–53].
Mg2Ni, which was formed by allying Mg with Ni, is widely re­
searched due to relatively low thermodynamic enthalpy and dehy­
drogenation temperature. [54–56] Specifically, hydriding combustion
synthesis, melting process, mechanical alloying, and high-pressure
torsion are frequently-used to synthesize Mg2Ni alloy. [57–61] For in­
stance, Li et al. [57,58] adopted hydriding combustion synthesis to
prepare Mg2Ni. X-ray diffraction (XRD) analysis found that hydriding
reaction could occur with a low hydrogen pressure of 1.0 MPa, but a
high temperature of 527 °C was required. Using the method of melting,
Mg2Ni could absorb 3.6 wt% and desorb 3.2 wt% hydrogen at 350 °C in
20 min, respectively. [62] Moreover, Si et al. [63,64] successfully syn­
thesized Mg2Ni by laser sintering and demonstrated pestle milling was
helpful for the formation of Mg2Ni. Recently, Sun et al. [65] fabricated
Mg2Ni by vacuum medium frequency induction melting and revealed
that the kinetics and thermodynamic performance of Mg2Ni was sig­
nificantly improved after the addition of Y and Cu. In detail, the des­
orption enthalpy (ΔH) and entropy (ΔS) of Mg2NiH4 composite could
be reduced to 61.1 kJ/mol and 115.4 J/k/mol, which were 6 kJ/mol and

https://doi.org/10.1016/j.jallcom.2022.164169
0925-8388/© 2022 Elsevier B.V. All rights reserved.
X. Lu, L. Zhang, J. Zheng et al.
Fig. 1. The schematic illustration of the synthesis of Mg2Ni particles.
Fig. 2. XRD patterns of as-prepared Mg2Ni.
7.7 J/k/mol lower than that of commercial Mg-based hydrides, re­
spectively.
Besides, the crystalline size of Mg2Ni and the addition of carbon
materials also affect its hydrogen storage performance. For instance,
Shao et al. [66] synthesized micro-sized Mg2Ni and nano-sized
Mg2Ni by hydrogen plasma-metal reaction method, and found nano-
szied Mg2Ni could be fully hydrogenated within 25 min at 350 °C,
but only 0.2 wt% H2 was absorbed for micro-sized Mg2Ni. Kou et al.
[67] found that the amorphous and nanocrystalline-Mg2Ni alloy
exhibited better absorption kinetics than that of crystalline- and
amorphous-Mg2Ni alloy. Later, carbon was evidenced effective to
enhance the kinetic performance of Mg2Ni alloy. In particular, Ma
et al. [68] studied the influence of graphene (G) for Mg2NiH4-TiH2
sample and found that the peak and onset dehydrogenation tem­
perature of Mg2NiH4-TiH2-G sample was lower than that of
Mg2NiH4-TiH2. Panda et al. [69] reported that the hydrogenated Mg-
2
Journal of Alloys and Compounds 905 (2022) 164169
Ni-reduced graphene oxide (rGO) composite exhibited fast dehy­
drogenation kinetics, which could desorb 4.5 wt% H2 at 320 °C
within 300 s while only 1.0 wt% H2 was released for the hydro­
genated Mg-Ni sample. In addition, the 0.5 mol% carbon nanotubes
modified Mg2Ni could release 3.26 wt% H2 within 100 min at 300 °C,
whereas pure Mg2Ni desorbed 3.20 wt% H2 within 120 min [70].
Our recent work revealed that wet chemical ball milling was
helpful to improve the action of hydrogen storage alloys towards the
de/absorption properties of MgH2. [71,72] Above references also
demonstrate that the preparation method plays an important role in
improving the hydrogen storage behavior of Mg2Ni. Thus, it is rea­
sonable to conjecture that Mg2Ni synthesized by wet-ball milling
method may present excellent hydrogen storage performance. To
figure out the combing effect of carbon and nanocrystalization on
the hydrogen storage of Mg2Ni, we constructed a carbon-covered
nanocrystalline Mg2Ni by a facile method of chemical ball milling
and heat treatment in this paper. The hydrogen ab/desorption ki­
netics, thermodynamic stability, and cycling performance of carbon-
covered nanocrystalline Mg2Ni were measured by a homemade
Sievert-type apparatus and differential scanning calorimeter (DSC)
equipment. The microstructure of samples was analyzed by XRD and
TEM measurements. Based on the above results, a specific hydrogen
storage mechanism was explored and proposed in detail.
2. Experiment details
2.1. Sample preparation
Mg2Ni alloys were prepared by a three-step method, including
sintering, mechanical ball milling, and wet chemical ball milling.
Magnesium powder (100–200 mesh; 99.8%, Sinopharm Chemical
Reagent Co, Shanghai, China) and nickel powder (200 mesh; 99.9%,
Sinopharm Chemical Reagent Co, Shanghai, China) were used as
starting materials. In brief, the mixture of Mg and Ni in an atomic
ratio of 2:1 was calcined at 600 °C for 2 h under an Ar atmosphere.
Next, the mixture was ball-milled (QM3SP4 Planetary Ball Mill)
at 400 rpm for 40 h with the ball to powder ratio of 80:1 (marked as
X. Lu, L. Zhang, J. Zheng et al.
Fig. 3. TEM images of Mg2Ni-A (a–b) and Mg2Ni-B (d–e), corresponding HRTEM image of Mg2Ni-A (c) and Mg2Ni-B (f).
Mg2Ni-A). Then, the mixture, oleic acid, oleamide, and n-heptane
with a volume ratio of 1: 0.33: 10: 20 were added to the ball-mill-jar
and further milled with a speed of 400 rpm for 40 h. [72,73] The
slurry was washed twice with n-heptane in a high-speed centrifuge
(8000 rpm, 10 min) to eliminate solvent factors. Finally, Mg2Ni
powders were obtained after being vacuumed at 250 °C for 3 h, la­
beled as Mg2Ni-B. The details of synthesis were illustrated in Fig. 1.
MgH2 was synthesized in our laboratory, and the particle size of the
as-prepared MgH2 was about 1 µm determined by the SEM
image. [72,74].
2.2. Characterization of Mg2Ni
An X′ Pert Pro X-ray diffractometer (XRD) with Cu Kα radiation
(λ = 1.5406 Å, 40 kV, 40 mA) was applied to characterize the phase
and structure information of the samples from 10 ° to 80 ° with a
scanning rate of 5 °/min. The transmission electron microscope
(TEM, Tecnai G2 F30 S-TWIN) was used to investigate the mor­
phology and microstructure of the samples. The thermal decom­
position of samples was performed by a Differential Scanning
Calorimeter (DSC, Shimadzu Thermal Analysis System/TA-60WS-
Japan) from room temperature to 500 °C at different heating rates (5,
8, 10, 12 K/min).
The de/absorption hydrogen behaviors of the samples were
quantitatively evaluated using a homemade Sievert-type apparatus.
For each test, about 150 mg powders were loaded in a reactor. Non-
isothermal dehydrogenation took place in a vacuum (~5 *10−3 Torr)
3
Journal of Alloys and Compounds 905 (2022) 164169
from ambient temperature to 450 °C at a heating rate of 2 °C/min,
whereas hydrogenation was performed in the temperature range of
20–400 °C with 1 °C/min under 3 MPa hydrogen pressure. The iso­
thermal measurements were carried out by rapidly heating the
samples to the preset temperature and then preserving the tem­
perature during the entire test. The equilibrium hydrogen pressures
were determined by the pressure-composites-temperature (PCT)
measurement. To avoid contamination, all the operations and
transferring were implemented in a MIKROUNA glove box filled
with Ar.
3. Results and discussion
3.1. Characterization of as-prepared Mg2Ni particles
To explore the microstructure of prepared Mg2Ni, XRD, TEM, and
high-resolution TEM (HRTEM) measurements were conducted. The
XRD patterns of the as-prepared samples are shown in Fig. 2. The
diffraction peaks of Mg2Ni-A and Mg2Ni-B could be indexed with the
standard pattern for Mg2Ni (PDF#35–1225). The average crystallite
size of Mg2Ni-A and Mg2Ni-B was calculated to be about 50 nm and
20 nm by using the Scherrer equation, respectively.
Fig. 3a and b show that the Mg2Ni-A sample consists of nano­
particles with an average diameter of 500 nm. Compared with the
Mg2Ni-A sample, the Mg2Ni-B sample exhibited a smaller particle
size, approaching 300 nm (Fig. 3d and e).
X. Lu, L. Zhang, J. Zheng et al.
Fig. 4. Non-isothermal absorption curves (a) of MgH2/Mg2Ni sample, isothermal absorption curves of MgH2 (b), Mg2Ni-A (c), Mg2Ni-B (d) (the ordinate was the fraction of
experiment vs. theoretical hydrogen content, MgH2 was 7.6 wt% and hydrogenated Mg2Ni was 3.6 wt%).
In addition, it was observed from Fig. 3f that the Mg2Ni-B sample
was covered with carbon. However, no carbon appeared in the
Mg2Ni-A sample (Fig. 3c). The carbon in the Mg2Ni-B sample might
be due to the carbonization of organic solvents during the heat
treatment at 250 °C, similar to a previous study. [75] Crystal­
lographic planes of Mg2Ni were observed from corresponding se­
lected area electron diffraction (SAED) patterns (Fig. 3a and d). The
HRTEM patterns presented in Fig. 3c and f further demonstrated that
the lattice spacing of 2.286 Å and 4.524 Å could be indexed as (106)
and (100) plane of Mg2Ni for the Mg2Ni-A sample and the Mg2Ni-B
sample, respectively. It can be seen from above results that the na­
nocrystalline Mg2Ni with and without carbon have been successfully
prepared.
3.2. Hydrogenation kinetics of as-prepared Mg2Ni
Fig. 4 present the hydrogenation curves of as-prepared Mg2Ni
samples. Hydrogen uptake took place at 30 °C for the prepared
Mg2Ni-A sample, and hydrogenation was saturated at 250 °C, su­
perior to that of dehydrogenated MgH2 (Fig. 4a). Encouragingly, the
Mg2Ni-B sample absorbed hydrogen at room temperature, and the
hydrogen absorption rate for the Mg2Ni-B sample was much faster
than that of the Mg2Ni-A sample before 200 °C. The hydrogen con­
tent of Mg2Ni-B was 86% of the theoretical value, lower than that of
Mg2Ni-A (98%). The decreased hydrogen content of Mg2Ni-B was due
4
Journal of Alloys and Compounds 905 (2022) 164169
to the presence of carbon [76,77]. Furthermore, the isothermal hy­
drogen absorption curves (Fig. 4b) showed that the dehydrogenated
MgH2 could absorb 59% of theoretical hydrogen content in 60 min at
210 °C, and 85% hydrogen could be charged when heated to 250 °C,
exhibiting relatively slow hydrogen absorption kinetics. At testing
temperature of 270 °C, the pure Mg sample showed fast hydro­
genation kinetics, releasing 92% capacity in the same duration. In
comparison, the hydrogenation kinetics was dramatically enhanced
by forming Mg2Ni alloy. In detail, the Mg2Ni-A sample was able to
absorb 18% H2 within just 60 min at a low temperature of 75 °C.
When hydrogenation was performed at 125 and 150 °C, it took only
60 min to take up 48% and 65% H2, respectively (Fig. 4c). It was in­
teresting to find that the hydrogen absorption rate and content of
the Mg2Ni-B sample were superior to those of the Mg2Ni-A sample,
suggesting that the Mg2Ni-B sample exhibited better hydrogen
sorption behavior under the same condition (Fig. 4c and d). For in­
stance, the Mg2Ni-B sample absorbed around 54% hydrogen in 1 h at
100 °C, much higher than 32% of the Mg2Ni-A sample, while the
dehydrogenated MgH2 hardly absorbed hydrogen. In addition, 44%
hydrogen could be charged even at a low temperature of 75 °C, and
59% and 68% absorption content could be achieved at 125 and 150 °C,
respectively. These results indicate that alloying is an effective
strategy to improve the hydrogen absorption property of Mg-based
materials. In addition, the smaller the grain size, the better hydrogen
absorption performance will be.
X. Lu, L. Zhang, J. Zheng et al.
Fig. 5. Isothermal hydrogenation JMAK curve plots of the prepared MgH2 (a), Mg2Ni-A (b), Mg2Ni-B (c), the fitted Arrhenius curve plots of MgH2 and Mg2Ni-A/B (d).
To further understand the improvement of hydrogenation ki­
netics, the absorption curves were fitted by Johnson-Mehl-Avrami-
Kolmogorov (JMAK) model: [78–80].
ln[-ln(1-α)] = ηln(k) + ηln(t)
where α represents the fraction of phase transformation from metal
to its hydride at time t, k and η correspond to a kinetic parameter
and the reaction order, respectively. The obtained results (Fig. 5a–c)
verified an excellent linear relationship between hydrogen absorp­
tion capacity and time by the above equation, and the corresponding
results could be applied to determine the absorption activation en­
ergy (Ea) using the Arrhenius equation (k = A exp (Ea /RT). According
to the lnk vs. 1000/T plots (Fig. 5d), the absorption Ea value of pure-
Mg was estimated to be 80.6 ± 5.0 kJ/mol (with R2 =0.98854).
The absorption Ea value for the Mg2Ni-A sample was calculated to be
44.9 ± 1.8 kJ/mol, 35.7 kJ/mol lower than that of pure Mg. The ab­
sorption Ea value was further decreased to 20.8 ± 1.2 kJ/mol for the
Mg2Ni-B sample. The remarkable decrease in Ea contributed to the
significantly improved hydrogenation kinetics of as-prepared Mg2Ni.
3.3. Dehydrogenation performance of Mg2NiH4
In order to further explore the hydrogen storage activity of MgH2
and Mg2NiH4, the non/-isothermal dehydrogenation kinetics was
also tested (Fig. 6). Fig. 6a reveals the non-isothermal dehy­
drogenation curves of MgH2 and Mg2NiH4 samples. The onset
Journal of Alloys and Compounds 905 (2022) 164169
dehydrogenation temperature of as-prepared MgH2 was 335 °C, and
upon heating to 385 °C, a total usable hydrogen capacity of 99% was
released, close to the theoretical content of 7.6 wt% in MgH2. The
initial dehydrogenation temperature of Mg2NiH4 was far lower than
(1)
that of pure-MgH2. In detail, the hydrogenated Mg2Ni-A sample
started to release hydrogen at approximately 240 °C. The onset de­
hydrogenation temperature of the hydrogenated Mg2Ni-B sample
was reduced to 180 °C, and 86% H2 capacity could be discharged
at 245 °C.
Isothermal dehydriding measurements were further conducted
for MgH2 and hydrogenated Mg2Ni-A/B samples at different tem­
peratures, as illustrated in Fig. 6(b-d). For MgH2, 83% hydrogen could
be released at 325 °C within 60 min. Raising the temperature to
350 °C, the dehydrogenation speed of MgH2 became faster. At 375 °C,
about 95% hydrogen could be desorbed in 10 min. The hydrogenated
Mg2Ni-A sample could desorb 21% H2 within 1 h at 250 °C and 99%
H2 at 275 °C in 15 min, respectively. All hydrogen was released from
the sample in 300 s at 300 °C. Compared to the dehydriding kinetics
of pure MgH2 and hydrogenated Mg2Ni-A sample, the hydrogenated
Mg2Ni-B sample presented better desorption kinetics. It can be seen
from Fig. 6d that the hydrogenated Mg2Ni-B sample showed good
dehydrogenation kinetics with a capacity of 42% within 1 h at the
lowest testing temperature of 200 °C. Under 250 °C, the hydro­
genated Mg2Ni-B sample released 86% H2 in 10 min, while only 21%
was released for the hydrogenated Mg2Ni-A sample.
The dehydrogenation apparent activation energy of Mg2NiH4 was
also calculated. The DSC profiles of the MgH2 and hydrogenated
5
X. Lu, L. Zhang, J. Zheng et al.
Fig. 6. Non-isothermal desorption curves (a) of MgH2 and Mg2NiH4 sample, isothermal desorption curves of MgH2 (b), hydrogenated Mg2Ni-A (c), and hydrogenated Mg2Ni-B (d)
at different temperatures.
Mg2Ni-A/B obtained at heating rates of 5, 8, 10, and 12 K/min and
corresponding Kissinger plots for desorption activation energy are
displayed in Fig. 7. The peak dehydrogenation temperature of the
hydrogenated Mg2Ni-B shifted to a lower one in comparison to
MgH2 and hydrogenated Mg2Ni-A. For example, the peak decom­
position temperature of the hydrogenated Mg2Ni-B sample was
184.7 °C (5 K/min), 193.1 and 65.4 °C lower than that of MgH2
(377.8 °C) and hydrogenated Mg2Ni-A (250.1 °C), respectively. The
apparent activation energy (Ea) for the dehydrogenation reaction of
MgH2 and hydrogenated Mg2Ni-A/B samples were estimated and
compared via the Kissinger method with the DSC data. The
Kissinger’s equation can be described as [71,79,81].
ln (β/Tm2) = - (Ea/(RTm)) + A
where β is the heating speed and Tm is the peak temperature, A is a
temperature-independent constant, and R is the standard atmo­
spheric constant. According to the linear fitting of ln(β/Tm2) vs. 1000/
Tm, the value of Ea for MgH2 was estimated to be 154.6 ± 16.3 kJ/mol.
The apparent activation energy for the hydrogenated Mg2Ni-B was
calculated to be 34.1 ± 2.4 kJ/mol, which was 119.6 and 54.6 kJ/mol
lower than that of MgH2 (154.6 ± 16.3 kJ/mol) and hydrogenated
Mg2Ni-A (89.0 ± 5.5 kJ/mol), respectively (Fig. 7b and d). By con­
structing carbon-covered Mg2NiH4 nanograins, the dehydrogenation
energy barrier could be greatly reduced, resulting in an enhanced
Journal of Alloys and Compounds 905 (2022) 164169
dehydrogenation kinetics.
To investigate the thermodynamic behavior of the hydrogenated
Mg2Ni-A/B samples, pressure-composition temperature (PCT) ex­
periments were carried out (Fig. 8). The dehydrogenation equili­
brium pressures of MgH2 at 325, 350, 375, and 400 °C were
determined to be 2.27, 4.19, 8.70, and 16.88 bar. It is noted that the
hydrogen deposition platform pressure obtained for the hydro­
genated Mg2Ni sample was slightly higher than reported MgH2
systems. In detail, the desorption plateaus of hydrogenated Mg2Ni-A
sample at 275, 300, 325, and 350 °C were 1.24, 2.35, 4.39, and
8.95 bar while those of hydrogenated Mg2Ni-B were measured to be
1.42, 2.66, and 4.88, and 8.27 bar for 275, 300, 325, and 350 °C,
respectively (Fig. 8c and e).
(2)
Based on the plateau pressures and corresponding Van’t Hoff
plots, the reaction enthalpy (ΔH) was calculated, shown in Fig. 8(b, d,
and f). The ΔH values of MgH2 and hydrogenated Mg2Ni-A were
estimated to be 89.9 ± 4.0 kJ/mol and 74.3 ± 3.5 kJ/mol. The ΔH
value of the hydrogenated Mg2Ni-B sample was further decreased to
67.0 ± 0.5 kJ/mol. As demonstrated previously, alloying [30,82–84]
was an efficient strategy to improve the thermodynamics of Mg-
based materials. Simultaneously, the addition of carbon also con­
tributed to the decrease of desorption enthalpy. [30] Thus, the hy­
drogenated Mg2Ni-B had a lower ΔH value, enabling it to release
hydrogen at a lower temperature.
6
X. Lu, L. Zhang, J. Zheng et al.
Fig. 7. DSC curves of as-prepared MgH2 (a) and hydrogenated Mg2Ni-A/B (c) at various heating rates (5, 8, 10, and 12 K/min) and the apparent activation energy of MgH2 (b) and
hydrogenated Mg2Ni-A/B (d).
3.4. Cycling property of Mg2NiH4 system
In order to further explore the cycling stability of Mg2NiH4,
successive hydrogen de/absorption measurements were executed.
As shown in Fig. 9, the cycling performance of Mg2Ni-A and Mg2Ni-B
samples was studied under 3 MPa hydrogen pressure at 275 °C. After
10 cycles, the kinetic performance and the content decreased slightly
for Mg2Ni-A (Fig. 9a). Specifically, the material could desorb 3.59 wt
% hydrogen at the first cycle, but only 3.32 wt% hydrogen was re­
leased after the 10th cycle. It was interesting that the Mg2Ni-B
sample presented stable cycling durability, and the hydrogen capa­
city showed almost no decline after the 10th cycle. In detail, the
Mg2Ni-B sample delivered a hydrogen capacity of 3.16 wt% in the
first dehydrogenation at 275 °C within 10 min, and it quickly as­
similated 3.16 wt% H2 at 275 °C within 45 s. After the 10 cycles, a high
reversible capacity of 3.08 wt% was maintained without degradation
of kinetics, which could give credit to the effect of carbon layers. It
was reported that carbon layers could help prevent the agglomera­
tion of Mg after multiple de/absorption experiments, resulting in
7
Journal of Alloys and Compounds 905 (2022) 164169
excellent cycling stability. [70,74,85–91] Thus, the outstanding ki­
netic performance of the Mg2Ni-B sample was proved again by cy­
cling behavior.
3.5. Modification mechanism
Based on the above investigations, the modification mechanism
of Mg2Ni/Mg2NiH4 for the enhanced de/hydrogenation properties
was discussed. In detail, by forming Mg2Ni alloy, the onset and peak
desorption temperature and hydrogen ab/-desorption kinetics were
remarkably improved. XRD and TEM results demonstrated that the
crystalline size in as-synthesized Mg2Ni-B sample was around
20 nm, and carbon covered the surface of Mg2Ni particles (as illu­
strated in Fig. 10). The inside nanocrystalline Mg2Ni provided nu­
merous diffusion channels and active sites for hydrogen to improve
the speed of hydrogenation and dehydrogenation. It should be
pointed out that the carbon would effectively decrease the binding
energy of Mg-based hydrides [92]. Meanwhile, carbon layers served
as guardians to control the nucleation and growth of Mg2Ni particles
X. Lu, L. Zhang, J. Zheng et al. Journal of Alloys and Compounds 905 (2022) 164169

Fig. 8. The pressure-composites-temperature (PCT) curves of MgH2 (a), hydrogenated Mg2Ni-A (c), and Mg2Ni-B (e) at different temperatures and corresponding Van’t Hoff plot
(b, d, and f).

8
X. Lu, L. Zhang, J. Zheng et al.
Fig. 9. Cycling profiles of Mg2Ni-A (a) and Mg2Ni-B (b) at 275 °C.
Fig. 10. Schematic hydrogenation and dehydrogenation for carbon covered nano­
crystalline Mg2Ni.
to maintain cyclic stability. Due to the combining effect of alloying,
carbon layers, and nanocrystalline, the de/-absorption temperature,
activation energy, and formation enthalpy of Mg2Ni were dramati­
cally decreased, resulting in an outstanding hydrogen storage per­
formance.
4. Conclusions
The present study provides a detailed investigation on the hy­
drogen storage property of carbon-covered nanocrystalline
Mg2NiH4. The onset dehydrogenation temperature of the hydro­
genated carbon-covered nanocrystalline Mg2NiH4 was 180 °C, which
was 60 °C and 155 °C lower than that of nanocrystalline Mg2NiH4
and MgH2, separately. Furthermore, the carbon-covered nanocrys­
talline Mg2NiH4 rapidly desorbed 3.1 wt% in 10 min at 250 °C and
started to absorb hydrogen even at room temperature. The peak
temperature and dehydrogenation activation energy for carbon-
covered nanocrystalline Mg2NiH4 could be decreased to 184.7 °C and
34.1 kJ/mol, respectively. A reversible capacity up to 3.1 wt% was well
maintained after 10 cycles at 275 °C. The hydrogen desorption ΔH of
the hydrogenated carbon-covered nanocrystalline Mg2NiH4 was
decreased from 89.9 ± 4.0 (MgH2) to 67.0 ± 0.5 kJ/mol. In conclu­
sion, this work offers a novel approach to synchronously enhance
the kinetic and thermodynamic behaviors of Mg-based hydrogen
storage systems for practical application in the future.
9
Journal of Alloys and Compounds 905 (2022) 164169
CRediT authorship contribution statement
Xiong Lu: Methodology, Software, Investigation, Data curation,
Writing – original draft, and replying the comments. Liuting Zhang:
Writing – review & editing, Conceptualization, and replying the
comments. Jiaguang Zheng: Validation, Software, Formal analysis.
Xuebin Yu: Resources, Conceptualization, Writing – review &
editing.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors would like to acknowledge financial support from
the National Key R&D Program of China (2020YFA0406204), the
National Natural Science Foundation of China (Grant No. 51801078),
the Natural Science Foundation of Jiangsu Province (Grant No.
BK20180986), and the Natural Science Foundation of Jiangsu
Province (Grant No. BK20210884).
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