Effect of SC Substitution On Hydrogen Storage P - 2015 - International Journal o
Effect of SC Substitution On Hydrogen Storage P - 2015 - International Journal o
Effect of SC Substitution On Hydrogen Storage P - 2015 - International Journal o
ScienceDirect
Jingbo Zhu a,b, Liqun Ma a,*, Fei Liang b, Limin Wang b,**
a
College of Material Science and Engineering, Nanjing Tech University, Nanjing 210009, China
b
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS,
Changchun 13002, China
* Corresponding author. Tel.: þ86 025 83587243; fax: þ86 025 83240205.
** Corresponding author. Tel./fax: þ86 0431 85262447.
E-mail addresses: [email protected] (L. Ma), [email protected] (L. Wang).
http://dx.doi.org/10.1016/j.ijhydene.2015.03.149
0360-3199/Copyright © 2015, 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 0 ( 2 0 1 5 ) 6 8 6 0 e6 8 6 5 6861
larger affinity with H and larger atomic radius than Ti, which
indicates that Sc substitution for Ti in TieV-based samples
may favor increasing the theoretical and effective hydrogen
storage capacity. Thus, we conducted a systematic research
on the microstructure, hydrogen storage properties of the Sc-
substituted TieVeCreMn samples. Besides, the Sc-
substituted TieVeCreMn system was reported for the first
time.
Experimental methods
Fig. 3 e SEM images of (40¡x)Tie40Ve10Cre10Mn-xSc: (a) x ¼ 0; (b) x ¼ 5; (c) x ¼ 10; (d) x ¼ 15.
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 0 ( 2 0 1 5 ) 6 8 6 0 e6 8 6 5 6863
Fig. 4 e Initial absorption kinetic curves of (40¡x) Fig. 5 e Optimal linear fitting of reaction mechanism
Tie40Ve10Cre10Mn-xSc (x ¼ 0, 5, 10, 15) at 273 K. equation with t: (a) x ¼ 0, 15; (b) x ¼ 5, 10.
contained sample, thus the lattice parameter of BCC phase in between P and t, we conducted the linear fitting of reaction
Sc-contained samples increases gradually. mechanism equations with t and held the equation with
maximum coefficient of determination (R2) as the kinetic
mechanism equation. The linear fitting results are shown in
Kinetic properties
Fig. 5.
R2 gets the maximum when gðaÞ ¼ ð1 aÞ1=2 for S0 and
Fig. 4 shows the initial hydrogen absorption kinetic curves of
S15, respectively 0.9992 and 0.9993. This equation belongs to
(40-x)Tie40Ve10Cre10Mn-xSc (x ¼ 0, 5, 10, 15) at 273 K. It was
chemical reaction mechanism. Moreover, the value of k is
found that the initial hydrogen absorption process could reach
respectively 2.377 and 2.113, indicating the reaction rate of the
the maximum hydrogen absorption capacity, indicating the
former is a little faster than the latter (only when kinetic
samples exhibit favorable activation properties. As it is shown
mechanism equations are the same, the value of k is
in Fig. 4, the hydrogen absorption capacity of Sc-free sample is
comparable).
larger than the Sc-contained samples and it increases gradu-
R2 gets the maximum when gðaÞ ¼ ½ð1 aÞ1=3 12 for S5
ally when x increases from 5 to 15, namely 3.587wt.%,
and gðaÞ ¼ ð1 aÞ2 for S10, respectively 0.9989 and 0.9985.
2.398wt.%, 2.903wt.%, 3.208wt.%. Moreover, it only takes 3.8,
These equations respectively belong to 3-D diffusion mecha-
4.3 min for S0 and S15, but 31.5, 42.1 min for S5 and S10 to
nism (S5) and chemical reaction mechanism (S10). Moreover,
reach the saturation of hydrogen absorption. The obvious re-
the value of k is respectively 0.220 and 15.605.
action rate's difference between S0, S15 and S5, S10 could be
In terms of S5, the lattice parameter of BCC phase is the
attributed to their different kinetic mechanisms which were
minimum (unfavorable for H atom's diffusion) and the
further studied as follows.
The gasesolid kinetic reaction function is [17]:
da
¼ kfðaÞ (1)
dt
Thus, we get the integration form of Eq. (1)
Z Z
da
¼ k$dt ¼ k$t (2)
fðaÞ
abundance of Laves phase is the maximum (Laves phase is capacity at 298 K showing consistent changing regulation
benefit for chemical reaction), which explains the kinetic when x increases from 5 to 15.
mechanism of S5 transforms to 3-D diffusion mechanism. As we can see in Fig. 6, the plateaus at 298 K cannot be
figured out obviously, which should be attributed to the
inhomogeneous chemical composition [19] and the low
PCI properties plateau pressure. Moreover, the hysteresis of absorption/
desorption PCI curves is improved with the Sc content
Fig. 6 shows the hydrogen absorption/desorption PCI curves of increasing. T. Kabutomori [20] had ever reported: because of
(40-x)Tie40Ve10Cre10Mn-xSc (x ¼ 0, 5, 10, 15) at 298 K. The good symmetry of the BCC structure, dislocations can be
hydrogen absorption capacity of Sc-free sample is larger than easily produced by deformation of the crystal during hydrogen
the Sc-contained samples and it increases gradually when x absorption/desorption process, which contributes to the
increases from 5 to 15, which is in accord with the changing hysteresis of absorption/desorption PCI curves. That is to say,
regulation of hydrogen absorption capacity at 273 K. However, Sc element may contribute to suppressing the production of
the hydrogen desorption capacity gradually increases when dislocations during hydrogen absorption/desorption process,
the Sc content increases. The detail hydrogen absorption/ thus improving the hysteresis of absorption/desorption PCI
desorption capacity at 298 K is listed in Table 3. curves.
According to Cho S W's report [7], hydrogen absorption/ As we can get from the van't Hoff equation, the variation of
desorption plateau pressure generally shows a converse temperature will not affect the changing regulation of plateau
changing regularity with lattice parameter. As we mentioned pressure (hereby, DSq is assumed as a constant, generally
before, the lattice parameter of BCC phase in Sc-free sample 130 J/(mol k)). Thus, to verify the changing regulation of
is larger than in Sc-contained samples and it increases plateau pressure at 298 K and to study the desorption prop-
gradually when x increases from 5 to 15. Thus, we can erties at higher temperature, we conducted the hydrogen
deduce: the hydrogen absorption/desorption plateau pres- desorption PCI testing at 373 K (after saturated hydrogen ab-
sure of Sc-free sample is smaller than Sc-contained samples sorption at 298 K).
and it decreases gradually when x increases from 5 to 15. As it is shown in Fig. 7, the hydrogen desorption plateau
This changing regulation of plateau pressure is also pressure of Sc-free sample is smaller than Sc-contained
confirmed by the next section of hydrogen desorption at samples and it decreases gradually when x increases from 5
373 K. Further, hydrogen absorption capacity generally shows to 15. Thereby, it confirms the changing regulation of plateau
a converse changing regulation with hydrogen absorption pressure we deduced at 298 K. As it is shown in Table 3, as the
plateau pressure, thus the hydrogen absorption capacity of Sc content increases, the changing regulation of hydrogen
Sc-free sample is larger than Sc-contained samples and it desorption capacity at 373 K is consistent with the changing
increases gradually when x increases from 5 to 15, showing regulation of hydrogen absorption capacity at 298 K. This
the consistent changing regulation with lattice parameter of phenomenon can be explained as follows: the cut-off pressure
BCC phase. is lower than the hydrogen desorption plateau pressure of all
Hydrogen desorption capacity is generally related to the samples at 373 K, thus hydrogen desorption capacity is
hydrogen desorption plateau pressure, cut-off pressure and mainly controlled by hydrogen absorption capacity, resulting
hydrogen absorption capacity. And the reason why S0 get the in hydrogen desorption capacity at 373 K and hydrogen ab-
minimum hydrogen desorption capacity should be explained sorption capacity at 298 K showing consistent changing
as follows: the cut-off pressure is higher than the hydrogen regulation.
desorption plateau pressure of S0 (whose plateau pressure is
the minimum), suppressing the hydrogen desorption reac-
tion, thus getting the minimum hydrogen desorption capac-
ity. Moreover, the reason why the hydrogen desorption
capacity increases when x increases from 5 to 15 should be
explained as follows: the cut-off pressure is lower than the
hydrogen desorption plateau pressure of Sc-contained sam-
ples, thus hydrogen desorption capacity is mainly controlled
by hydrogen absorption capacity, resulting in hydrogen
desorption capacity at 298 K and hydrogen absorption