Characterization of Hydrogen-Storage Properties and Physical Properties of Zinc Borohydride and Transition Metals-Added Magnesium Hydride

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VOLUME 23 , ISSUE 1 (March 2017) > List of articles

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Characterization of Hydrogen-Storage Properties and Physical Properties of Zinc Borohydride and Transition Metals-Added Magnesium Hydride

Young Jun Kwak / Hye Ryoung Park / Myoung Youp Song *

Keywords : hydrogen absorbing materials , ball milling , scanning electron microscopy (SEM) , X-ray diffraction , Ni , Zn(BH4)2 , Fe , Ti-added MgH2-based alloy.

Citation Information : Materials Science. VOLUME 23 , ISSUE 1 , Pages 32-38 , ISSN (Online) 2029–7289, DOI: 10.5755/j01.ms.23.1.14878, March 2017 © 2017.

License : (CC-BY-4.0)

Received Date : 29-April-2016 / Accepted: 02-September-2016 / Published Online: 2017

ARTICLE

ABSTRACT

In this work, 90 wt.% MgH2+5 wt.% Ni+1.7 wt.% Zn(BH4)2+1.7 wt.% Ti+1.7 wt.% Fe samples (named 90MgH2+5Ni+ +1.7Zn(BH4)2+1.7Ti+1.7Fe) were prepared by milling in a planetary ball mill in a hydrogen atmosphere. The fraction of additives was small (10 wt.%) in order to increase hydriding and dehydriding rates without decreasing the hydrogen storage capacity much. The hydrogen absorption and release properties of the prepared samples were investigated. 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe had an effective hydrogen storage capacity of 5 wt.%. The activation of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe was completed after 2 hydriding-dehydriding cycles. At n = 3, the sample absorbed 4.14 wt.% H for 5 min and 5.00 wt.% H for 60 min at 593 K under 12 bar H2. The sample dehydrided at the 3rd hydriding-dehydriding cycle contained Mg and small amounts of β-MgH2, MgO, Mg2Ni, TiH1.924, and Fe. The BET specific surface areas of the sample after milling in a hydrogen atmosphere and after 3 hydriding-dehydriding cycles were 57.9 and 53.2 m2/g, respectively.

Graphical ABSTRACT

1. Introduction

Magnesium hydride, which draws attention as a hydrogen storage material, has high gravimetric hydrogen density and is inexpensive and abundant in the earth’s crust [1]. However, its reaction rates with hydrogen are very low. Many researchers tried to increase the hydriding and dehydriding rates of magnesium [24] by alloying certain metals [59] with it and synthesizing compounds such as CeMg12 [10].

Many researches [1120] were performed on metal borohydrides [M(BH4)n] as promising candidates for advanced hydrogen storage materials due to their high specific volumetric hydrogen-storage capacities. The complex metal hydride Zn(BH4)2 has also drawn attention due to its high specific volumetric hydrogen-storage capacity (8.4 wt.%) [2124] and low decomposition temperature (323 – 393 K).

Bobet et al. [8] reported that mechanical grinding in H2 of magnesium powder converted Mg to MgH2 partially. Its conversion ratio could be improved by increasing the milling time or by adding a 3d-element. Shahi et al. [25] mechanically milled MgH2 with transition metals (Ti, Fe, and Ni). They reported that the decomposition temperature of MgH2 was reduced and the rehydrogenation kinetics was correspondingly enhanced.

In the present work, Zn(BH4)2, Ni, Ti, and Fe were selected to be added in order to improve the hydriding and dehydriding rates of magnesium. In our previous works [26], a Zn(BH4)2 sample was prepared by milling ZnCl2 and NaBH4 in a planetary ball mill in an Ar atmosphere. A simultaneous addition of Zn(BH4)2, Ni, Ti, and Fe is expected to lead to refining of MgH2 particles since brittle Zn(BH4)2 and hard Ni, Fe, and Ti particles will help the MgH2 particles be milled with effect. Ni is known to form Mg2NiH4, which has higher hydriding and dehydriding rates than magnesium [27]. A relatively large percentage (5 wt.%) of Ni was added to increase the dehydriding rate of MgH2. Small percentages of Zn(BH4)2, Ti, and Fe were added not to decrease the fraction of MgH2 too much so that the prepared sample may have a large hydrogen-storage capacity.

90wt.% MgH2+5wt.% Ni+1.7wt.% Zn(BH4)2+1.7wt.% Ti+ +1.7 wt.% Fe samples (named 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe) were prepared by milling in a planetary ball mill in a hydrogen atmosphere. The fraction of additives was small (10 wt.%) in order to increase hydriding and dehydriding rates without decreasing the hydrogen storage capacity significantly. The hydrogen absorption and release properties of the prepared samples were investigated. In addition, the physical properties, such as microstructure, particle size distribution, and BET (Brunauer-Emmett-Teller) specific surface area, of the samples after milling in hydrogen and after hydriding-dehydriding cycling were examined.

2. Experimental Details

The starting materials were MgH2 (Magnesium hydride, Aldrich, hydrogen-storage grade), Ni (Nickel powder, Alfa Aesar, average particle size 2.2 – 3.0 μm, 99.9 % (metals basis), C typically < 0.1), Ti (Titanium powder, Aldrich, – 325 mesh ( – 0.044 mm), 99 % (metals basis)), Fe (Alfa Aesar GmbH (Germany), Iron particle size < 10 μm, purity 99.9 %), and Zn(BH4)2 prepared in our previous works [26].

Milling in hydrogen of a mixture with a composition of 90 wt.% MgH2+5 wt.% Ni+1.7 wt.% Zn(BH4)2+ 1.7 wt.% Ti+ +1.7 wt.% Fe (total weight = 8 g) was performed in a planetary ball mill (Planetary Mono Mill; Pulverisette 6, Fritsch), which has a hermetically-sealed stainless steel container (with 105 hardened steel balls, total weight = 360 g). The sample to ball weight ratio was 1:45. Samples were handled in a glove box under Ar to prevent oxidation. The disc revolution speed was 400 rpm. The mill container (volume of 250 ml) was filled with high purity hydrogen gas (≈ 12 bar). Milling in hydrogen was performed for 2 h [28].

The variations, with time, of the quantities of hydrogen absorbed and released by the prepared samples were measured under the hydrogen pressures maintained nearly constant, using a Sievert’s type hydriding and dehydriding apparatus, as described previously [29]. X-ray diffraction (XRD) patterns for the prepared samples were obtained using a Rigaku D/MAX 2500 powder diffractometer with Cu Kα radiation (diffraction angle range 10 – 80°, scan speed 4°/min). The microstructures of the samples after milling in hydrogen and after hydriding-dehydriding cycling were observed using a scanning electron microscope (SEM, JEOL JSM-6400) operated at 20 kV. Particle size distributions and BET specific surface areas of the samples were analyzed using UPA-150 (Microtrac, USA) and ASAP2010 (Micrometrics, USA), respectively.

3. Results

Fig. 1 shows the SEM micrographs of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe after milling in a hydrogen atmosphere. The particle size of the sample is not homogeneous. The sample has small particles, large particles, and agglomerates. The surfaces of some agglomerates are quite flat. Milling in hydrogen of MgH2 with Ni, Zn(BH4)2, Ti, and Fe is considered to create defects on the surface and in the inside of MgH2 particles, to produce reactive clean surfaces, and to reduce the particle size of MgH2.

Fig. 1.

SEM micrographs of 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe after milling in hydrogen

10.5755_j01.ms.23.1.14878-f1.jpg

The XRD pattern of 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe after milling in hydrogen is shown in Fig. 2. The sample contains β-MgH2, γ-MgH2, Ni, Ti, Fe, and MgO. β-MgH2, having a tetragonal structure, is a low pressure form of MgH2. γ-MgH2, having an orthorhombic structure, is one of the high pressure forms of MgH2. This shows that γ-MgH2 is formed during milling in a hydrogen atmosphere even under the low hydrogen pressure of about 12 bar. A small amount of MgO is formed. In this XRD pattern, the background is quite high and the peaks are broad, demonstrating the slightly noncrystalline nature of the sample after milling in hydrogen. The phases related to Zn(BH4)2 are not detected. This is believed to be since the small quantity of Zn(BH4)2 is contained in the sample and they may appear at the diffraction angles similar to those of other phases. The quite high back ground also makes difficult the appearance of weak diffraction lines.

Fig. 2.

XRD pattern of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe after milling in hydrogen

10.5755_j01.ms.23.1.14878-f2.jpg

The percentage of absorbed hydrogen, Ha, is expressed with respect to sample weight. Fig. 3 shows the variation of the Ha vs. t curve and the log Ha vs. t curve of 90MgH2 + 5Ni + 1.7Zn(BH4)2 + 1.7Ti + 1.7Fe at 593 K under 12 bar H2 with the number of cycles, n. From n = 1, the initial hydriding rate is very high, and becomes low after about 10 min. As the number of cycles increases from 1 to 3, the initial hydriding rate increases. The quantity of hydrogen absorbed for 60 min, Ha(60 min), increases from n = 1 to n = 2 and decreases from n = 2 to n = 3. At n = 1, the sample absorbs 3.82 wt.% H for 5 min and 4.93 wt.% H for 60 min. At n = 3, the sample absorbs 4.14 wt.% H for 5 min and 5.00 wt.% H for 60 min. The log Ha vs. t curve enables us to distinguish data points clearly. Fig. 3 b shows plainly that the initial hydriding rate increses as the number of cycles increases. Table 1 presents the variation of the absorbed hydrogen quantity with time for 90MgH2 + 5Ni + 1.7Zn(BH4)2 + 1.7Ti + 1.7Fe at 593 K under 12 bar H2 at n = 1 – 3.

Fig. 3.

Variations of (a) the Ha vs. t curve and (b) the log Ha vs. t curve of 90MgH2 + 5Ni + 1.7 Zn(BH4)2 + 1.7Ti + 1.7Fe at 593 K under 12 bar H2 with the number of cycles, n

10.5755_j01.ms.23.1.14878-f3.jpg
Table 1.

Variation of the absorbed hydrogen quantity with time for 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe at 593 K under 12 bar H2 at n = 1 3

Absorbed hydrogen quantity (wt.% H)

 

2.5 min

5 min

10 min

15 min

60 min

n = 1

2.95

3.82

4.71

4.85

4.93

n = 2

3.05

3.94

4.84

4.92

5.05

n = 3

3.13

4.14

4.70

4.92

5.00

The percentage of desorbed hydrogen, Hd, is also expressed with respect to the sample weight. The variation of the Hd vs. t curve of 90MgH2 + 5Ni + 1.7Zn(BH4)2+ + 1.7Ti + 1.7Fe at 593 K under 1.0 bar H2 with the number of cycles, n, is shown in Fig. 4. The initial dehydriding rate is quite high, and becomes low after about 40 min. At n = 2 and n = 3, the initial dehydriding rate is higher and the quantity of hydrogen desorbed for 60 min is larger than those at n = 1. At n = 2 and n = 3, the initial dehydriding rate and the quantity of hydrogen desorbed for 60 min are nearly similar. At n = 1, the sample desorbs 1.46 wt.% H for 10 min and 4.57 wt.% H for 60 min. At n = 3, the sample desorbs 1.77 wt.% H for 10 min and 4.67 wt.% H for 60 min. Table 2 presents the variation of the desorbed hydrogen quantity with time for 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe at 593 K under 1.0 bar H2 at n = 1 and n = 3.

Fig. 4.

Variation of the Hd vs. t curve of 90MgH2+5Ni+ +1.7Zn(BH4)2+1.7Ti+1.7Fe at 593 K under 1.0 bar H2 with the number of cycles, n

10.5755_j01.ms.23.1.14878-f4.jpg
Table 2.

Variation of the desorbed hydrogen quantity with time for 90MgH2 + 5Ni + 1.7Zn(BH4)2 + 1.7Ti + 1.7Fe at 593 K under 1.0 bar H2 at n = 1 and n = 3

Desorbed hydrogen quantity (wt.% H)

 

5 min

10 min

20 min

30 min

60 min

n = 1

0.84

1.46

2.68

3.53

4.57

n = 3

1.05

1.77

3.00

4.02

4.67

Fig. 3 and Fig. 4 show that the activation of 90MgH2+ +5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe is completed after 2 hydriding-dehydriding cycles.

Fig. 5 shows the SEM micrographs of 90MgH2 + 5Ni+ +1.7Zn(BH4)2+1.7Ti+1.7Fe dehydrided at the 3rd hydriding-dehydriding cycle. The particle size of the sample is not homogeneous. The sample has small particles, large particles, and agglomerates. The surfaces of some agglomerates are rounded. Particles got rounded and slightly larger, compared with those after milling in hydrogen.

Fig. 5.

SEM micrographs of 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7 Ti+1.7Fe dehydrided at the 3rd hydriding-dehydriding cycle

10.5755_j01.ms.23.1.14878-f5.jpg

The XRD pattern of 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe dehydrided at the 3rd hydriding-dehydriding cycle is shown in Fig. 6. This sample has better crystallinity than the as-milled sample. The sample contains Mg and small amounts of β-MgH2, MgO, Mg2Ni, TiH1.924, and Fe. This shows that Mg2Ni formed from the reaction of Ni with Mg, and TiH1.924 formed by the reaction of Mg with hydrogen and is undecomposed even after dehydriding reaction.

Fig. 6.

XRD pattern of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe dehydrided at the 3rd hydriding-dehydriding cycle

10.5755_j01.ms.23.1.14878-f6.jpg

Particle size distribution analysis results of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe after milling in hydrogen and after 3 hydriding-dehydriding cycles are shown in Fig. 7. The particle size distribution curves exhibit high peaks at about 0.01 and 0.7 μm for the sample after milling in hydrogen and a high peak at about 1.2 μm for the sample after 3 hydriding-dehydriding cycles. The sample after 3 hydriding-dehydriding cycles has larger particles than the sample after milling in hydrogen. The average particle size of the sample after milling in hydrogen was analyzed as 0.85 μm and that of the sample after 3 hydriding-dehydriding cycles was analyzed as 1.34 μm.

Fig. 7.

Particle size distribution analysis results of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe (a) after milling in hydrogen and (b) after 3 hydriding-dehydriding cycles

10.5755_j01.ms.23.1.14878-f7.jpg

The BET plots of 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe after milling in hydrogen and after 3 hydriding-dehydriding cycles are shown in Fig. 8. P and Po are the equilibrium and the saturation pressure of adsorbates at the temperature of adsorption, and Va is the adsorbed gas quantity (for example, in volume units). The BET specific surface area of the sample after milling in a hydrogen atmosphere is 57.9 m2/g and that of the sample after 3 hydriding-dehydriding cycles is 53.2 m2/g.

Fig. 8.

BET plots of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe after milling in hydrogen and after 3 hydriding-dehydriding cycles

10.5755_j01.ms.23.1.14878-f8.jpg

Fig. 9 shows the Ha vs. t curves under 12 bar H2 at n = 1 for unmilled MgH2 [30], unmilled Mg [31], and 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe at 593 K and 94MgH2+6Ni [28] at 573 K. The 94MgH2 + 6Ni sample was prepared by milling in a hydrogen atmosphere under the conditions similar to those for the preparation of the 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe sample.

Fig. 9.

Ha vs. t curves under 12 bar H2 at n = 1 for unmilled MgH2, unmilled Mg, and 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe at 593 K and 94MgH2+6Ni at 573 K

10.5755_j01.ms.23.1.14878-f9.jpg

Unmilled MgH2 absorbs hydrogen extremely slowly and unmilled Mg absorbs hydrogen slowly. 94MgH2+6Ni and 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe have much higher initial hydriding rates and much larger quantities of hydrogen absorbed for 60 min than unmilled MgH2 and unmilled Mg. 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe has a larger initial hydriding rate and quantity of hydrogen absorbed for 60 min than 94MgH2 + 6Ni. Unmilled MgH2 absorbs 0.04 wt.% H for 60 min. Unmilled Mg absorbs 0.20 wt.% H for 10 min and 0.51 wt.% H for 60 min. 94MgH2+6Ni absorbs 3.14 wt.% H for 10 min and 3.48 wt.% H for 60 min. 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe absorbs 4.71 wt.% H for 10 min and 4.93 wt.% H for 60 min. Table 3 presents the variation of the absorbed hydrogen quantity with time for unmilled MgH2, unmilled Mg, and 90MgH2+5Ni+ +1.7Zn(BH4)2+1.7Ti+1.7Fe at 593 K and 94MgH2 + 6Ni at 573 K under 12 bar H2 at n = 1.

Table 3.

Variation of the absorbed hydrogen quantity with time under 12 bar H2 at n = 1 for unmilled MgH2, unmilled Mg, and 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe at 593 K and 94MgH2 + 6Ni at 573 K

Absorbed hydrogen quantity (wt.% H)

 

2.5 min

5 min

10 min

15 min

25 min

60 min

Unmilled MgH2

0

 

 

 

 

0.04

Unmilled Mg

0.09

0.10

0.20

0.26

0.34

0.51

94MgH2+6Ni

2.30

2.81

3.14

3.26

3.35

3.48

90MgH2+5Ni++1.7Zn(BH4)2++1.7Ti+1.7Fe

 

3.82

4.71

4.85

 

4.93

4. Discussion

The XRD pattern of 78.3 wt.% Zn(BH4)2 + 21.7 wt.% MgH2 after being heated up to 643 K showed that the sample contained NaCl, Zn, and MgH2 [26]. NaCl was formed during synthesis of Zn(BH4)2 by milling ZnCl2 and NaBH4 [21]. This XRD pattern shows that Zn is formed by the decomposition of Zn(BH4)2 during heating. Nakagawa et al. [21] reported that Zn(BH4)2 releases hydrogen with toxic diborane (B2H6) after melting with increasing temperature. These indicate that Zn(BH4)2 decomposes into Zn, B2H6, and H2 during heating.

For the measurements of hydriding and dehydriding properties, the sample was heated to 673 K and gases were released by pumping with a vacuum pump. It is thought that, during this time, NaCl, TiH1.924, and Fe remain un-reacted, and the following reaction occurs:

(1)
Zn(BH4)2+xMgH2+yNiZn+B2H6+yMg2Ni+(x2y)Mg+(x+1)H2,
where x and y are stoichiometric coefficients.

During the subsequent hydriding-dehydriding cycling of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe, Zn, NaCl, TiH1.924, and Fe remain un-reacted. Thus, during the subsequent hydriding-dehydriding cycling of this sample, the hydriding and dehydriding reactions of Mg and Mg2Ni occur.

The SEM micrograph of Mg particles showed that the Mg particles are large and have smooth surfaces with a very small number of cracks [31]. The SEM micrographs of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe after milling in a hydrogen atmosphere, presented in Fig. 1, show that the particle size of the sample is not homogeneous and the sample has small particles, large particles, and agglomerates. Compared with Mg particles, 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe particles have more defects and much smaller particle sizes. The BET specific surface area of the sample after milling in hydrogen was 57.9 m2/g and that of the as-prepared 94MgH2+6Ni sample was 37.6 m2/g [28]. This shows that addition of Zn(BH4)2, Ti, and Fe increases the BET specific surface area. The average particle sizes of unmilled MgH2 [30], unmilled Mg [31], 94MgH2+6Ni [28], and 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe were 0.65, 0.25, 0.83, and 0.85 μm. 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe does not have the smallest average particle size, but it has the highest initial hydriding rate and the largest value of Ha(60 min). The initial hydriding rate and the value of Ha(60 min) are not proportional to the decrease in the average particle size of the sample. This means that, in addition to the average particle size, other factors such as number of defects and cleanness of the particle surfaces determine the initial hydriding rate and the value of Ha(60 min). The milling in a hydrogen atmosphere of MgH2 with Ni, Zn(BH4)2, Fe, and Ti is thus believed to increase the hydriding and dehydriding rates by producing defects [3234] on the surface and in the inside of particles, generating newly exposed clean surfaces [34, 35], and decrease the particle size of MgH2 [32, 3538]. The production of defects facilitates nucleation, generating newly exposed clean surfaces improves the reactivity of surfaces, and the decrease of the particle size reduces the diffusion distances of hydrogen atoms [3941]. These effects are believed to increase the hydriding and dehydriding rates of MgH2.

Mg2Ni has much higher hydriding and dehydriding rates than Mg at about 573 K [27]. The Mg2Ni phase formed after hydriding-dehydriding cycling is also believed to increase the hydriding and dehydriding rates of MgH2.

TiH1.924, Fe, Zn, NaCl, and MgO, remaining un-reacted during hydriding-dehydriding cycling, are believed to prevent the particles from being coalesced during hydriding-dehydriding cycling.

90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe has an effective hydrogen-storage capacity (the quantity of hydrogen absorbed for 60 min) of 5 wt.%.

In the sample after 3 hydriding-dehydriding cycles, particles are larger (Fig. 5), has a larger average particle size (Fig. 7), and has a smaller BET specific surface area (Fig. 8), compared with those in the sample after milling in hydrogen. It is believed that particles become larger due to coalescence of particles because hydriding-dehydriding cycling was performed at a relatively high temperature of 593 K.

5. Conclusions

90wt.%MgH2+5wt.%Ni+1.7wt.% Zn(BH4)2+ 1.7 wt.% Ti+1.7wt.%Fe samples (named 90MgH2+5Ni+ +1.7Zn(BH4)2+1.7Ti+1.7Fe) were prepared by milling in a planetary ball mill in a hydrogen atmosphere. 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe had an effective hydrogen storage capacity of 5 wt.%. The activation of the sample was completed after 2 hydriding-dehydriding cycles. The as-milled 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe sample contained β-MgH2, γ-MgH2, Ni, Ti, Fe, and MgO. The sample dehydrided at the 3rd hydriding-dehydriding cycle contained Mg and small amounts of β-MgH2, MgO, Mg2Ni, TiH1.924, and Fe. The BET specific surface area of the sample after milling in hydrogen was 57.9 m2/g and that of the sample after 3 hydriding-dehydriding cycles was 53.2 m2/g. At n = 3, the sample absorbed 4.14 wt.% H for 5 min and 5.00 wt.% H for 60 min at 593 K under 12 bar H2. At n = 3, the sample desorbed 1.77 wt.% H for 10 min and 4.67 wt.% H for 60 min at 593 K under 1.0 bar H2. The milling in a hydrogen atmosphere of MgH2 with Ni, Zn(BH4)2, Ti, and Fe is believed to facilitate nucleation, improve the reactivity of surfaces, and reduce the diffusion distances of hydrogen atoms.

Acknowledgments

This research was supported by a grant (2013 Ha A17) from Jeonbuk Research & Development Program funded by Jeonbuk Province.

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    Renaudin, G., Gomes, S., Hagemann, H., Keller, L., Yvon, K. Structural and Spectroscopic Studies on the Alkali Borohydrides MBH4 (M = Na, K, Rb, Cs) Journal of Alloys and Compounds 375 2004: pp. 98 – 106. https://doi.org/10.1016/j.jallcom.2003.11.018
    [CROSSREF] [URL]
  15. 15.
    Yoshino, M., Komiya, K., Takahashi, Y., Shinzato, Y., Yukawa, H., Morinaga, M. Nature of the Chemical Bond in Complex Hydrides, NaAlH4, LiAlH4, LiBH4 and LiNH2 Journal of Alloys and Compounds 404 – 406 2005: pp. 185-190.
  16. 16.
    Orimo, S., Nakamori, Y., Kitahara, G., Miwa, K., Ohba, N., Towata, S., Züttel, A. Dehydriding and Rehydriding Reactions of LiBH4 Journal of Alloys and Compounds 404 – 406 2005: pp. 427 – 430.
  17. 17.
    Kang, J.K., Kim, S.Y., Han, Y.S., Muller, R.P., Goddard, W.A. A Candidate LiBH4 for Hydrogen Storage: Crystal Structures and Reaction Mechanisms of Intermediate Phases Applied Physics Letters 87 2005: pp. 111904 – 111904-3.
    [CROSSREF]
  18. 18.
    Kumar, R.S., Cornelius, A.L. Structural Transitions in NaBH4 under Pressure Applied Physics Letters 87 2005: pp. 261916 – 261916-3.
    [CROSSREF]
  19. 19.
    Nakamori, Y., Miwa, K., Ninomiya, A., Li, H.W., Ohba, N., Towata, S., Züttel, A., Orimo, S. Correlation between Thermodynamical Stabilities of Metal Borohydrides and Cation Electronegativites: First-Principles Calculations and Experiments Physical Review B 74 2006: pp. 045126.
    [CROSSREF]
  20. 20.
    Nakamori, Y., Li, H.W., Miwa, K., Towata, S., Orimo, S. Syntheses and Hydrogen Desorption Properties of Metal-Borohydrides M(BH4)n (M= Mg, Sc, Zr, Ti, and Zn; n=2-4) as Advanced Hydrogen Storage Materials Materials Transactions 47 (8) 2006: pp. 1898 – 1901.
    [CROSSREF]
  21. 21.
    Nakagawa, T., Ichikawa, T., Kojima, Y., Fujii, H. Gas Emission Properties of the MgHx-Zn(BH4)2 Systems Materials Transactions 48 (3) 2007: pp. 556 – 559. https://doi.org/10.2320/matertrans.48.556
    [CROSSREF] [URL]
  22. 22.
    Setamdideh, D., Khaledi, L. Zn(BH4)2/2NaCl: A Novel Reducing System for Efficient Reduction of Organic Carbonyl Compounds to Their Corresponding Alcohols South African Journal of Chemistry 66 2013: pp. 150 – 157.
  23. 23.
    Jeon, E., Cho, Y.W. Mechanochemical Synthesis and Thermal Decomposition of Zinc Borohydride Journal of Alloys and Compounds 422 2006: pp. 273 – 275.
    [CROSSREF]
  24. 24.
    Jeon, E., Cho, Y.W. Synthesis and Thermal Decomposition of Zn(BH4)2 Transactions of the Korean Hydrogen and New Energy Society 16 2005: pp. 262 – 268.
  25. 25.
    Shahi, R.R., Tiwari, A.P., Shaz, M.A., Srivastava, O.N. Studies on De/Rehydrogenation Characteristics of Nanocrystalline MgH2 Co-Catalyzed with Ti, Fe and Ni International Journal of Hydrogen Energy 6 2013: pp. 2778 – 2784. https://doi.org/10.1016/j.ijhydene.2012.11.073
    [CROSSREF] [URL]
  26. 26.
    Kwak, Y.J., Kwon, S.N., Song, M.Y. Preparation of Zn(BH4)2 and Diborane and Hydrogen Release Properties of Zn(BH4)2+xMgH2 (x=1, 5, 10, and 15) Metals and Materials International 21 2015: pp. 971 – 976. https://doi.org/10.1007/s12540-015-4604-6
    [CROSSREF] [URL]
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    Akiba, E., Nomura, K., Ono, S., Suda, S. Kinetics of the reaction between Mg-Ni alloys and H2 International Journal of Hydrogen Energy 7 1982: pp. 787 – 791. https://doi.org/10.1016/0360-3199(82)90069-6
    [CROSSREF] [URL]
  28. 28.
    Kwak, Y.J., Lee, S.H., Park, H.R., Song, M.Y. Hydrogen-Storage Property Enhancement of Magnesium Hydride by Nickel Addition via Reactive Mechanical Grinding Korean Journal of Metals and Materials 51 2013: pp. 607 – 613.
    [CROSSREF]
  29. 29.
    Song, M.Y., Baek Bobet, J.L., Song, J., Hong, S.H. Hydrogen Storage Properties of a Mg–Ni–Fe Mixture Prepared via Planetary Ball Milling in a H2 Atmosphere International Journal of Hydrogen Energy 35 2010: pp. 10366 – 10372. https://doi.org/10.1016/j.ijhydene.2010.07.161
    [CROSSREF] [URL]
  30. 30.
    Song, M.Y., Kwak, Y.J., Lee, S.H., Park, H.R. Comparison of Hydrogen Storage Properties of Pure MgH2 and Pure Mg Korean Journal of Metals and Materials 52 2014: pp. 689 – 693.
    [CROSSREF]
  31. 31.
    Song, M.Y., Kwak, Y.J., Lee, S.H., Park, H.R. Comparison of the Hydrogen Storage Properties of Pure Mg and Milled Pure Mg Bulletin of Materials Science 37 2014: pp. 831 – 835.
    [CROSSREF]
  32. 32.
    Song, M.Y., Ivanov, E.I., Darriet, B., Pezat, M., Hagenmuller, P. Hydriding and Dehydriding Characteristics of Mechanically Alloyed Mixtures Mgxwt.%Ni (x = 5, 10, 25, and 55) Journal of the Less-Common Metals 131 1987: pp. 71 – 79. https://doi.org/10.1016/0022-5088(87)90502-9
    [CROSSREF] [URL]
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    Vigeholm, B., Kjoller, J., Larsen, B., Pedersen, A.S. Formation and Decomposition of Magnesium Hydride Journal of the Less-Common Metals 89 1983: pp. 135 – 144. https://doi.org/10.1016/0022-5088(83)90259-X
    [CROSSREF] [URL]
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    Jain, I.P., Lal, C., Jain, A. Hydrogen Storage in Mg: A Most Promising Material International Journal of Hydrogen Energy 35 2010: pp. 5133 – 5144. https://doi.org/10.1016/j.ijhydene.2009.08.088
    [CROSSREF] [URL]
  35. 35.
    David, E. Nanocrystalline Magnesium and its Properties of Hydrogen Sorption Journal of Achievements in Materials and Manufacturing Engineering 20 2007: pp. 87 – 90.
  36. 36.
    Spassov, T., Delchev, P., Madjarov, P., Spassova, M., Himitliiska, T. Hydrogen Storage in Mg–10 at.% LaNi5 Nanocomposites, Synthesized by Ball Milling at Different Conditions Journal of Alloys and Compounds 495 2010: pp. 149 – 153.
    [CROSSREF]
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    Zaluska, A., Zaluski, L., Ström-Olsen, J.O. Nanocrystalline Magnesium for Hydrogen Storage Journal of Alloys and Compounds 288 1999: pp. 217 – 225.
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    Aguey-Zinsou, K.F., Ares Fernandez, J.R., Klassen, T., Bormann, R. Using MgO to Improve the (De)Hydriding properties of magnesium Materials Reearch Bulletin 41 2006: pp. 1118 – 1126.
    [CROSSREF]
  39. 39.
    Hong, S.H., Song, M.Y. MgH2 and Ni-Coated Carbon-Added Mg Hydrogen-Storage Alloy Prepared by Mechanical Alloying Korean Journal of Metals and Materials 54 2016: pp. 125 – 131.
    [CROSSREF]
  40. 40.
    Hong, S.H., Song, M.Y. Study on the Reactivity with Hydrogen of Planetary Ball Milled 90 wt.% Mg + 10 wt.% MgH2: Analyses of Reaction Rates with Hydrogen and Microstructure Korean Journal of Metals and Materials 54 2016: pp. 358 – 363.
    [CROSSREF]
  41. 41.
    Kwak, Y.J., Kwon, S.N., Song, M.Y. Hydriding and Dehydriding properties of Zinc Borohydride, Nickel, and Titanium-Added Magnesium Hydride Korean Journal of Metals and Materials 53 2015: pp. 808 – 814.
    [CROSSREF]
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FIGURES & TABLES

Fig. 1.

SEM micrographs of 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe after milling in hydrogen

Full Size   |   Slide (.pptx)

Fig. 2.

XRD pattern of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe after milling in hydrogen

Full Size   |   Slide (.pptx)

Fig. 3.

Variations of (a) the Ha vs. t curve and (b) the log Ha vs. t curve of 90MgH2 + 5Ni + 1.7 Zn(BH4)2 + 1.7Ti + 1.7Fe at 593 K under 12 bar H2 with the number of cycles, n

Full Size   |   Slide (.pptx)

Fig. 4.

Variation of the Hd vs. t curve of 90MgH2+5Ni+ +1.7Zn(BH4)2+1.7Ti+1.7Fe at 593 K under 1.0 bar H2 with the number of cycles, n

Full Size   |   Slide (.pptx)

Fig. 5.

SEM micrographs of 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7 Ti+1.7Fe dehydrided at the 3rd hydriding-dehydriding cycle

Full Size   |   Slide (.pptx)

Fig. 6.

XRD pattern of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe dehydrided at the 3rd hydriding-dehydriding cycle

Full Size   |   Slide (.pptx)

Fig. 7.

Particle size distribution analysis results of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe (a) after milling in hydrogen and (b) after 3 hydriding-dehydriding cycles

Full Size   |   Slide (.pptx)

Fig. 8.

BET plots of 90MgH2+5Ni+1.7Zn(BH4)2+1.7Ti+1.7Fe after milling in hydrogen and after 3 hydriding-dehydriding cycles

Full Size   |   Slide (.pptx)

Fig. 9.

Ha vs. t curves under 12 bar H2 at n = 1 for unmilled MgH2, unmilled Mg, and 90MgH2+5Ni+1.7Zn(BH4)2+ +1.7Ti+1.7Fe at 593 K and 94MgH2+6Ni at 573 K

Full Size   |   Slide (.pptx)

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    Yoshino, M., Komiya, K., Takahashi, Y., Shinzato, Y., Yukawa, H., Morinaga, M. Nature of the Chemical Bond in Complex Hydrides, NaAlH4, LiAlH4, LiBH4 and LiNH2 Journal of Alloys and Compounds 404 – 406 2005: pp. 185-190.
  16. 16.
    Orimo, S., Nakamori, Y., Kitahara, G., Miwa, K., Ohba, N., Towata, S., Züttel, A. Dehydriding and Rehydriding Reactions of LiBH4 Journal of Alloys and Compounds 404 – 406 2005: pp. 427 – 430.
  17. 17.
    Kang, J.K., Kim, S.Y., Han, Y.S., Muller, R.P., Goddard, W.A. A Candidate LiBH4 for Hydrogen Storage: Crystal Structures and Reaction Mechanisms of Intermediate Phases Applied Physics Letters 87 2005: pp. 111904 – 111904-3.
    [CROSSREF]
  18. 18.
    Kumar, R.S., Cornelius, A.L. Structural Transitions in NaBH4 under Pressure Applied Physics Letters 87 2005: pp. 261916 – 261916-3.
    [CROSSREF]
  19. 19.
    Nakamori, Y., Miwa, K., Ninomiya, A., Li, H.W., Ohba, N., Towata, S., Züttel, A., Orimo, S. Correlation between Thermodynamical Stabilities of Metal Borohydrides and Cation Electronegativites: First-Principles Calculations and Experiments Physical Review B 74 2006: pp. 045126.
    [CROSSREF]
  20. 20.
    Nakamori, Y., Li, H.W., Miwa, K., Towata, S., Orimo, S. Syntheses and Hydrogen Desorption Properties of Metal-Borohydrides M(BH4)n (M= Mg, Sc, Zr, Ti, and Zn; n=2-4) as Advanced Hydrogen Storage Materials Materials Transactions 47 (8) 2006: pp. 1898 – 1901.
    [CROSSREF]
  21. 21.
    Nakagawa, T., Ichikawa, T., Kojima, Y., Fujii, H. Gas Emission Properties of the MgHx-Zn(BH4)2 Systems Materials Transactions 48 (3) 2007: pp. 556 – 559. https://doi.org/10.2320/matertrans.48.556
    [CROSSREF] [URL]
  22. 22.
    Setamdideh, D., Khaledi, L. Zn(BH4)2/2NaCl: A Novel Reducing System for Efficient Reduction of Organic Carbonyl Compounds to Their Corresponding Alcohols South African Journal of Chemistry 66 2013: pp. 150 – 157.
  23. 23.
    Jeon, E., Cho, Y.W. Mechanochemical Synthesis and Thermal Decomposition of Zinc Borohydride Journal of Alloys and Compounds 422 2006: pp. 273 – 275.
    [CROSSREF]
  24. 24.
    Jeon, E., Cho, Y.W. Synthesis and Thermal Decomposition of Zn(BH4)2 Transactions of the Korean Hydrogen and New Energy Society 16 2005: pp. 262 – 268.
  25. 25.
    Shahi, R.R., Tiwari, A.P., Shaz, M.A., Srivastava, O.N. Studies on De/Rehydrogenation Characteristics of Nanocrystalline MgH2 Co-Catalyzed with Ti, Fe and Ni International Journal of Hydrogen Energy 6 2013: pp. 2778 – 2784. https://doi.org/10.1016/j.ijhydene.2012.11.073
    [CROSSREF] [URL]
  26. 26.
    Kwak, Y.J., Kwon, S.N., Song, M.Y. Preparation of Zn(BH4)2 and Diborane and Hydrogen Release Properties of Zn(BH4)2+xMgH2 (x=1, 5, 10, and 15) Metals and Materials International 21 2015: pp. 971 – 976. https://doi.org/10.1007/s12540-015-4604-6
    [CROSSREF] [URL]
  27. 27.
    Akiba, E., Nomura, K., Ono, S., Suda, S. Kinetics of the reaction between Mg-Ni alloys and H2 International Journal of Hydrogen Energy 7 1982: pp. 787 – 791. https://doi.org/10.1016/0360-3199(82)90069-6
    [CROSSREF] [URL]
  28. 28.
    Kwak, Y.J., Lee, S.H., Park, H.R., Song, M.Y. Hydrogen-Storage Property Enhancement of Magnesium Hydride by Nickel Addition via Reactive Mechanical Grinding Korean Journal of Metals and Materials 51 2013: pp. 607 – 613.
    [CROSSREF]
  29. 29.
    Song, M.Y., Baek Bobet, J.L., Song, J., Hong, S.H. Hydrogen Storage Properties of a Mg–Ni–Fe Mixture Prepared via Planetary Ball Milling in a H2 Atmosphere International Journal of Hydrogen Energy 35 2010: pp. 10366 – 10372. https://doi.org/10.1016/j.ijhydene.2010.07.161
    [CROSSREF] [URL]
  30. 30.
    Song, M.Y., Kwak, Y.J., Lee, S.H., Park, H.R. Comparison of Hydrogen Storage Properties of Pure MgH2 and Pure Mg Korean Journal of Metals and Materials 52 2014: pp. 689 – 693.
    [CROSSREF]
  31. 31.
    Song, M.Y., Kwak, Y.J., Lee, S.H., Park, H.R. Comparison of the Hydrogen Storage Properties of Pure Mg and Milled Pure Mg Bulletin of Materials Science 37 2014: pp. 831 – 835.
    [CROSSREF]
  32. 32.
    Song, M.Y., Ivanov, E.I., Darriet, B., Pezat, M., Hagenmuller, P. Hydriding and Dehydriding Characteristics of Mechanically Alloyed Mixtures Mgxwt.%Ni (x = 5, 10, 25, and 55) Journal of the Less-Common Metals 131 1987: pp. 71 – 79. https://doi.org/10.1016/0022-5088(87)90502-9
    [CROSSREF] [URL]
  33. 33.
    Vigeholm, B., Kjoller, J., Larsen, B., Pedersen, A.S. Formation and Decomposition of Magnesium Hydride Journal of the Less-Common Metals 89 1983: pp. 135 – 144. https://doi.org/10.1016/0022-5088(83)90259-X
    [CROSSREF] [URL]
  34. 34.
    Jain, I.P., Lal, C., Jain, A. Hydrogen Storage in Mg: A Most Promising Material International Journal of Hydrogen Energy 35 2010: pp. 5133 – 5144. https://doi.org/10.1016/j.ijhydene.2009.08.088
    [CROSSREF] [URL]
  35. 35.
    David, E. Nanocrystalline Magnesium and its Properties of Hydrogen Sorption Journal of Achievements in Materials and Manufacturing Engineering 20 2007: pp. 87 – 90.
  36. 36.
    Spassov, T., Delchev, P., Madjarov, P., Spassova, M., Himitliiska, T. Hydrogen Storage in Mg–10 at.% LaNi5 Nanocomposites, Synthesized by Ball Milling at Different Conditions Journal of Alloys and Compounds 495 2010: pp. 149 – 153.
    [CROSSREF]
  37. 37.
    Zaluska, A., Zaluski, L., Ström-Olsen, J.O. Nanocrystalline Magnesium for Hydrogen Storage Journal of Alloys and Compounds 288 1999: pp. 217 – 225.
    [CROSSREF]
  38. 38.
    Aguey-Zinsou, K.F., Ares Fernandez, J.R., Klassen, T., Bormann, R. Using MgO to Improve the (De)Hydriding properties of magnesium Materials Reearch Bulletin 41 2006: pp. 1118 – 1126.
    [CROSSREF]
  39. 39.
    Hong, S.H., Song, M.Y. MgH2 and Ni-Coated Carbon-Added Mg Hydrogen-Storage Alloy Prepared by Mechanical Alloying Korean Journal of Metals and Materials 54 2016: pp. 125 – 131.
    [CROSSREF]
  40. 40.
    Hong, S.H., Song, M.Y. Study on the Reactivity with Hydrogen of Planetary Ball Milled 90 wt.% Mg + 10 wt.% MgH2: Analyses of Reaction Rates with Hydrogen and Microstructure Korean Journal of Metals and Materials 54 2016: pp. 358 – 363.
    [CROSSREF]
  41. 41.
    Kwak, Y.J., Kwon, S.N., Song, M.Y. Hydriding and Dehydriding properties of Zinc Borohydride, Nickel, and Titanium-Added Magnesium Hydride Korean Journal of Metals and Materials 53 2015: pp. 808 – 814.
    [CROSSREF]

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