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The hydrogen storage properties and reaction mechanism of the MgH2eNaAlH4 composite system
M. Ismail a,b, Y. Zhao a,c,*, X.B. Yu a,d,*, J.F. Mao a, S.X. Dou a
a

Institute for Superconducting and Electronic Materials, University of Wollongong, Northelds Ave, Wollongong, NSW 2519, Australia Department of Physical Sciences, Faculty of Science and Technology, Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Malaysia c School of Mechanical, Materials and Mechatronics Engineering, University of Wollongong, NSW 2522, Australia d Department of Materials Science, Fudan University, Shanghai 200433, China
b

article info
Article history: Received 14 February 2011 Received in revised form 5 April 2011 Accepted 17 April 2011 Available online 18 May 2011 Keywords: MgH2 NaAlH4 Absorption/desorption Perovskite-type hydride

abstract
In this study, we report the hydrogen absorption/desorption properties and reaction mechanism of the MgH2eNaAlH4 (4:1) composite system. This composite system showed improved dehydrogenation performance compared with that of as-milled NaAlH4 and MgH2 alone. The dehydrogenation process in the MgH2eNaAlH4 composite can be divided into four stages: NaAlH4 is rst reacted with MgH2 to form a perovskite-type hydride, NaMgH3 and Al. In the second dehydrogenation stage, the Al phase reacts with MgH2 to form Mg17Al12 phase accompanied with the self-decomposition of the excessive MgH2. NaMgH3 goes on to decompose to NaH during the third dehydrogenation stage, and the last stage is the decomposition of NaH. Kissinger analysis indicated that the apparent activation energy, EA, for the MgH2-relevent decomposition in MgH2eNaAlH4 composite was 148 kJ/mol, which is 20 kJ/mol less than for as-milled MgH2 (168 kJ/mol). X-ray diffraction patterns indicate that the second, third, and fourth stages are fully reversible. It is believed that the formation of Al12Mg17 phase during the dehydrogenation process alters the reaction pathway of the MgH2eNaAlH4 (4:1) composite system and improves its thermodynamic properties. Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Because it is a promising energy carrier, intensive efforts have been made to realize the potential of hydrogen to become a major energy carrier, for both mobile and stationary applications. Solid-state hydrogen storage has become an attractive option due to its high volumetric hydrogen capacity and favorable safety considerations. Its large hydrogen storage capacity (7.6 wt.%), low cost, and superior reversibility make MgH2 a promising candidate for on-board hydrogen storage

[1e6]. However, the high thermodynamic stability and slow desorption kinetics [7,8] constrain the practical application of MgH2. Many studies have been conducted to overcome these problems, such as by preparing nanocrystalline Mg powder [7] and adding catalysts [8e10]. Besides the studies mentioned above, the destabilization concept was also introduced [11,12]. The destabilization concept could be regarded as a quite different approach. This approach is aimed at modifying the thermodynamics and kinetics of the hydrogen sorption reaction. Thermodynamic destabilization is achieved

* Corresponding authors. Institute for Superconducting and Electronic Materials, University of Wollongong, Northelds Ave, Wollongong, NSW 2519, Australia. Fax: 61 2 4221 5731. E-mail addresses: yue@uow.edu.au (Y. Zhao), yuxuebin@fudan.edu.cn (X.B. Yu). 0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2011.04.132

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using additives that form a new compound during dehydrogenation. Vajo et al. [13] tried to use certain elements such as Si to destabilize MgH2. The formation of an intermediate phase, Mg2Si, during the dehydrogenation process is benecial to MgH2 destabilization. However, the formation of Mg2Si would reduce the gravimetric hydrogen density because Si cannot be hydrogenated, so this intermediate phase seems hard to make reversible. Motivated by the studies of Vajo et al., many elements have been mixed with MgH2, including LiBH4 [14e18], NaBH4 [19e21], LiAlH4 [22e25], and Li3AlH6 [26]. Recently Zhang et al. [22] reported that MgH2 can be destabilized effectively by LiAlH4 in which the onset dehydrogenation temperature and the enthalpies of MgH2-relevent decomposition in MgH2eLiAlH4 composite is improved from that of as-milled MgH2. In addition, Chen et al. [24] also demonstrated that the combination of MgH2 and LiAlH4 by mechanical grinding reduced the decomposition temperature of MgH2. Both articles claimed that the formation of Al12Mg17 as a reaction product during the dehydrogenation process play a main catalytic effect in the MgH2eLiAlH4 composite systems. Another potential element to destabilize MgH2 is NaAlH4. Varin et al. [27] studied the morphology and the reaction mechanism in an MgH2 73 vol.% NaAlH4 composite system by scanning electron microscopy (SEM) and differential scanning calorimetry. Sartori et al. [28] further reported the reaction mechanism and hydrogen released from NaAlH4 MgH2 Al prepared by hydrogenating a mixture of 2MgH2 3Al NaH under 160 bar and 80  C for 12 h. However, the hydrogen storage performances of an MgH2eNaAlH4 composite system have not been thoroughly investigated so far. It is also necessary to verify whether the role of NaAlH4 is similar to the role of LiAlH4 in the MgH2eLiAlH4 composite system, since NaAlH4 and LiAlH4 are from the same alanate family. In the present paper, we investigated the hydrogen storage properties and the reaction pathways of the MgH2eNaAlH4 (4:1) composite system during the de/rehydrogenation process through temperature programmed desorption (TPD), Thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), isothermal sorption measurements and X-ray diffraction (XRD) measurements. The reaction mechanism of MgH2eNaAlH4 (4:1) composite was discussed based on our experimental results.

direction at the rate of 400 rpm. Pure MgH2 and NaAlH4 were also prepared under the same conditions for comparison purposes. The experiments for de/rehydrogenation were performed in a Sieverts-type pressure-composition-temperature (PCT) apparatus (Advanced Materials Corporation). The sample was loaded into a sample vessel in the glove box. For the TPD experiment, all the samples were heated in a vacuum chamber, and the amount of desorbed hydrogen was measured to determine the lowest decomposition temperature. The heating rate for the TPD experiment was 5  C min1, and samples were heated from room temperature to 450  C. The re/dehydrogenation kinetics measurements were performed at the desired temperature with initial hydrogen pressures of 3.0 MPa and 0.001 MPa, respectively. XRD analysis was performed using a GBC MMA X-ray diffractometer with Cu Ka radiation. qe2q scans were carried out over diffraction angles from 25 to 80 with a speed of 2.00  /min. Before the measurement, a small amount of sample was spread uniformly on the sample holder, which was wrapped with plastic wrap to prevent oxidation. Thermogravimetric analysis/differential scanning calorimetry (TGA/DSC) of the dehydrogenation process was carried out on a Mettler Toledo TGA/DSC 1. The sample was loaded into an alumina crucible in the glove box. The crucible was then placed in a sealed glass bottle in order to prevent oxidation during transportation from the glove box to the TGA/DSC apparatus. An empty alumina crucible was used for reference. The samples were heated from room temperature to 500  C under an argon ow of 30 ml/min, and different heating rates were used.

3.

Results and discussion

2.

Experimental

Pure MgH2 (hydrogen storage grade) and NaAlH4 (hydrogen storage grade, 93% purity) were purchased from SigmaeAldrich and were used as received with no further purication. Approximately 2 g of a mixture of MgH2 and NaAlH4 with a molar ratio of 4:1 was loaded into a sealed stainless steel vial together with hardened stainless steel balls in an argon atmosphere MBraun Unilab glove box. For simplicity, the mixture of MgH2 and NaAlH4 with molar ratio of 4:1 will be referred to as MgH2eNaAlH4 composite. The ratio of the weight of balls to the weight of powder was 40:1. The sample was then milled in a planetary ball mill (QM-3SP2) for 1 h, by rst milling for 0.5 h, resting for 6 min, and then milling for another 0.5 h in a different

Fig. 1 displays the TPD curves of the as-milled MgH2, the asmilled NaAlH4, and the MgH2eNaAlH4 composite. The asmilled MgH2 starts to release hydrogen at 330  C and desorbs about 7.1 wt.% H2 after 420  C. Meanwhile, the as-milled NaAlH4 releases about 5.5 wt.% hydrogen in the dehydrogenation temperature range between 180  C and 285  C. For the MgH2eNaAlH4 composite, it is believed that there are four stages of dehydrogenation occurring during the heating process. The four stages of dehydrogenation process are reported by Sartori et al. [28] for the dehydrogenation process of hydrogenating 2MgH2 3Al NaH under 160 bar and 80  C for 12 h. The rst stage, which takes place within the temperature range from 170 to 212  C, is attributed to the reaction: NaAlH4 MgH2 /NaMgH3 Al 1:5H2 (1)

In order to clarify the dehydrogenation mechanism, XRD was used. From the Fig. 2(a), it can be seen that, MgH2 and NaAlH4 phases are detected in the as-milled MgH2eNaAlH4 composite. Fig. 2(b) shows the XRD pattern of the MgH2eNaAlH4 composite after dehydrogenation at 212  C. Clearly, the pattern indicates the presence of perovskite-type hydride, NaMgH3 and Al besides the unreacted MgH2. The fact that no NaAlH4 phase was found indicates that the Eq. (1) reaction was completed at this stage. From the result we can

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from a mixing decomposition of (i) the reaction of MgH2 with Al and (ii) the decomposition of the excessive MgH2. This kind of MgH2-relevent decomposition can be speculated to be through the reaction in Eqs. (2) and (3), which occurs at a temperature 50  C lower than the decomposition temperature of the as-milled MgH2. 17MgH2 12Al/Mg17 Al12 17H2 MgH2 /Mg H2 (2) (3)

Fig. 1 e TPD (temperature programmed desorption) curves of the as-milled MgH2, the as-milled NaAlH4, and the MgH2eNaAlH4 composite. (I, II, III, and IV refer to the rst, second, third, and fourth dehydrogenation stage, respectively).

Further heating led to the third decomposition, starting at 330  C and completed at 360  C, corresponding to the decomposition of NaMgH3, as shown in Eq. (4). The last stage dehydrogenation is due to the decomposition of NaH, with decomposition starting at 360  C and ending at 375  C (Eq. (5)). XRD measurements at 360 and 375  C were carried out to clarify these dehydrogenation stages. As shown in Fig. 2(d) and (e), the peaks of NaH appear after dehydrogenation at 360  C, and the peaks of Na can be detected after further heating to 375  C. These results indicated that the reactions of Eqs. (4) and (5) occurred in the third and fourth stages, respectively. NaMgH3 /NaH Mg H2 NaH/Na 1=2H2 (4) (5)

see that the decomposition temperature of NaAlH4 in the MgH2eNaAlH4 composite reduced by 10  C compared with that of as-milled NaAlH4 indicating that the dehydrogenation performance of NaAlH4 is slightly improved after combining with MgH2. The second dehydrogenation stage, starting at about 280  C and completed at about 330  C, can be attributed to the MgH2 or NaMgH3-relevent decomposition. In order to investigate the reaction progress and mechanism, XRD measurements were performed on the MgH2eNaAlH4 composite after dehydrogenation at 330  C. As can be seen from the XRD result (Fig. 2(c)), the peaks for MgH2 and Al disappear, and new peaks corresponding to Mg17Al12 and Mg are observed. Furthermore, the peaks for NaMgH3 still remain unchanged. These results demonstrate that the hydrogen released in the second stage is

Fig. 3 compares the isothermal dehydrogenation kinetics of MgH2 NaMgH3 in the MgH2eNaAlH4 composite at 300  C and 320  C. The dehydrogenation of MgH2 was also examined for comparison under the same conditions. The dehydrogenation kinetics test was carried out after a rehydrogenation process under w3 MPa of H2 at 300  C. At 320  C, the MgH2eNaAlH4 sample desorbed about 3.5 wt.% hydrogen after 12 min, which is much higher than for the MgH2 (desorbed about 0.4 wt.% hydrogen). Meanwhile, after 12 min dehydrogenation, the MgH2eNaAlH4 sample released about 1.2 wt.% hydrogen at 300  C, but the MgH2 only released about 0.2 wt.% hydrogen at the same time and temperature. It is important to note that the dehydrogenation kinetics of the MgH2eNaAlH4 sample at

Fig. 2 e XRD patterns of the MgH2eNaAlH4 composite (a) after 1 h ball milling and after dehydrogenation at (b) 212  C, (c) 330  C, (d) 360  C, and (e) 375  C.

Fig. 3 e Isothermal dehydrogenation kinetics of the MgH2 and the MgH2eNaAlH4 composite at 300  C and 320  C.

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300  C is much faster than the dehydrogenation kinetics of the MgH2 at 320  C. This result indicates that the MgH2-relevant dehydrogenation kinetics is signicantly improved after combining with NaAlH4. Fig. 4 presents the TGA/DSC traces of the MgH2eNaAlH4 composite and the as-milled MgH2, which is also shown for comparison (inset plot). For the MgH2eNaAlH4 composite, the rst endothermic peak at 185  C corresponds to the melting of NaAlH4 [29], and the second endothermic peak at 275  C corresponds to the reaction of NaAlH4 and MgH2 (rst stage dehydrogenation). Note that, before the rst endothermic peak, there is an extra exothermic peak. This exothermic peak at 170  C is most probably due to the presence of surface hydroxyl impurities in the powder as reported in our previous paper [30,31] for LiAlH4. Furthermore, after the second endothermic (rst stage dehydrogenation), three overlapping endothermic reactions occurred due to the decomposition of MgH2, NaMgH3 and NaH. The rst overlapping endothermic peak at 363  C can be ascribed to MgH2relevent decomposition (second stage dehydrogenation), and the rest are due to the decomposition of NaMgH3 and NaH (third and fourth stage dehydrogenation). Ikeda et al. [32] reported that there are two overlapping endothermic reactions accompanying with continuous weight-loss in the decomposition of NaMgH3 and NaH. Compared to the asmilled MgH2 (inset plot), the temperature of the MgH2-relevent decomposition in the MgH2eNaAlH4 composite is clearly decreased. It starts to release hydrogen at about 315  C, 50  C below the temperature for the as-milled MgH2 (365  C). This decrease in the hydrogen release temperature is correlated to the results observed in the PCT measurement (Fig. 1). From the TGA/DSC results, it can be seen that the decomposition temperatures of the as-milled MgH2 and the MgH2eNaAlH4 composite are higher than those from the Sieverts-type PCT results (Fig. 1). This difference may be due

to the different heating rates and the different heating atmospheres between the two measurements. The activation energy, EA, for the hydrogen desorption mechanism of the MgH2eNaAlH4 composite was obtained by performing a Kissinger analysis [33], according to the following equation: h i ln b=T2 p EA =RTp A (6)

where b is the heating rate, Tp is the peak temperature in the DSC curve, R is the gas constant, and A is a linear constant. Thus, the activation energy, EA, can be obtained from the slope in a plot of ln[b/Tp2] versus 1000/Tp. Fig. 5 shows DSC traces for the MgH2eNaAlH4 composite at different heating rates (b 10, 15, and 20  C min1, respectively). All the peaks in the MgH2eNaAlH4 composite were shifted when the heating rates increased. The inset of Fig. 5 shows a Kissingers plot of the dehydrogenation reaction for the MgH2eNaAlH4 composite as compared with the as-milled MgH2. (The plot refers to the MgH2-relevent decomposition, the rst of the overlapping endothermic peaks). The apparent activation energy, EA, estimated from the Kissinger analysis for the MgH2-relevent decomposition in MgH2eNaAlH4 composite is found to be 148 kJ/mol, which is lower than for the as-milled MgH2 (168 kJ/mol). This indicates that mixing with NaAlH4 reduced the activation energy and thus improved the dehydrogenation behavior of MgH2. To investigate the reversibility of MgH2eNaAlH4 composite, the rehydrogenation of the dehydrogenated sample was performed under w3 MPa of H2 at 300  C. The MgH2 system was also examined for comparison. Fig. 6 compares the isothermal rehydrogenation kinetics of the MgH2eNaAlH4 composite and the MgH2. From the results, the MgH2eNaAlH4 sample shows slow absorption kinetics compared with the MgH2. After 30 min, the MgH2eNaAlH4 sample has just absorbed 5.1 wt.% hydrogen relative to the MgH2 sample, which can absorb as much as 6.1 wt.% hydrogen.

Fig. 4 e TGA/DSC traces of the MgH2eNaAlH4 composite and the inset plot is TGA/DSC traces of the as-milled MgH2. Heating rate: 15  C minL1, argon ow: 30 ml/min. (I, II, III, and IV refer to the rst, second, third, and fourth dehydrogenation stages).

Fig. 5 e DSC traces of MgH2eNaAlH4 composite at different heating rates. The inset plot is the Kissingers analysis for (a) as-milled MgH2 and (b) MgH2eNaAlH4 composite.

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Mg2 Al3 2H2 /2MgH2 3Al

(8)

Fig. 6 e Isothermal rehydrogenation kinetics of the MgH2eNaAlH4 composite and the MgH2 samples at 300  C and under 3 MPa.

Fig. 7 displays the XRD patterns of the MgH2eNaAlH4 composite after rehydrogenation under w3 MPa of H2 at 300  C. From the patterns, it can be seen that the peaks correspond to MgH2, NaMgH3, Al and a small peak for Al3Mg2 that appears after rehydrogenation. No NaAlH4 peak was detected. The NaMgH3 phase conrms that reactions (4) and (5) are reversible, as reported by Ikeda et al. [32]. After rehydrogenation, the Mg17Al12 peaks disappear, and peaks of MgH2, Al, and small peaks of Al3Mg2 appear, indicating that Mg17Al12 can be dissociated into Mg2Al3, MgH2, and Al (Eq. (7)) as reported by Yabe and Kuji [34], and Zhang and Wu [35]. Mg17 Al12 17 2yH2 /yMg2 Al3 17 2yMgH2 12 3yAl (7)

In this study, Mg2Al3 was hardly to transform into MgH2 and Al due to the lower hydrogenation pressure applied (3 MPa). This phenomenon is similar to that reported by Zhang et al. [22] for MgH2eLiAlH4 (4:1) composite, in which their sample was rehydrogenated under 4 MPa. For comparison, Chen et al. [24] reported that no Mg2Al3 phase was detected from their MgH2eLiAlH4 (4:1) composite sample after rehydrogenation at 350  C and under 10 MPa, implying that reaction (8) occurred when the higher hydrogen pressure was applied. The slow absorption kinetics in the MgH2eNaAlH4 composite may due to the yield of Mg2Al3. From the results, it can be pointed out that the role of NaAlH4 in this study is quite similar to the role of LiAlH4 in the MgH2eLiAlH4 composite system. The formation of Mg17Al12 phase as a reaction product of MgH2 with Al during the dehydrogenation process may create a benecial pathway for hydrogen atom diffusion to the surface and recombination, while it improves the thermodynamic properties of the MgH2eNaAlH4 composite system, as reported by Zhang et al. [22] and Chen et al. [24] for the MgH2eLiAlH4 (4:1) composite. Besides Mg17Al12 phase, Zhang et al. [22] also claimed that a catalytic effect may also be contributed by Li0.92Mg4.08 phase, which is formed as a reaction product of MgH2 with LiH during the dehydrogenation process in the MgH2eLiAlH4 composite system. In our study, the reaction of MgH2 with NaAlH4 formed a perovskite-type hydride, NaMgH3, and this product may also play a catalytic role in enhancement of the dehydrogenation behavior of MgH2eNaAlH4 composite. This hypothesis is still under investigation and will be presented in a further report.

4.

Conclusion

If higher hydrogenation pressure were applied, Mg2Al3 would subsequently be transformed into MgH2 and Al, as shown in Eq. (8) [36]:

Fig. 7 e XRD patterns of the MgH2eNaAlH4 composite after rehydrogenation at 300  C and under 3 MPa.

In summary, we have demonstrated that the hydrogen desorption properties of MgH2 were improved after mixing with NaAlH4. From the TPD results, the MgH2 in the composite starts to release hydrogen at about 280  C, compared with 330  C for as-milled MgH2. This composite also showed strong improvement in the dehydrogenation kinetics. The TPD results show that the dehydrogenation process in the MgH2eNaAlH4 (4:1) composite can be divided into four stages: the rst dehydrogenation stage can be attributed to the reaction of NaAlH4 and MgH2. The second dehydrogenation stage is due to the MgH2 react with Al accompanied with the selfdecomposition of excessive MgH2; the third dehydrogenation stage can be ascribed to the decomposition of NaMgH3; and the last dehydrogenation stage is due to the decomposition of NaH. The Kissinger plots for different heating rates in DSC show that the apparent activation energy, EA, for decomposition of MgH2-relevent in the MgH2eNaAlH4 (4:1) composite is reduced to 148 kJ/mol compared with 168 kJ/mol for the asmilled MgH2. We believe that the formation of Mg17Al12 phase during the dehydrogenation process plays a critical role in the enhancement of dehydrogenation in MgH2eNaAlH4 composite. However, the rehydrogenation measurements revealed that the MgH2eNaAlH4 (4:1) composite did not show any improvement compared with the as-milled MgH2.

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Acknowledgments
The authors thank the University of Wollongong for nancial support of this research. M. Ismail acknowledges the Ministry of Higher Education Malaysia for a PhD scholarship. Many thanks also go to Dr. T. Silver for critical reading of the manuscript.

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