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1 Phase Transformations in MgH2–TiH2 Hydrogen Storage

2 System by High-Pressure Torsion Process
3 Kouki Kitabayashi, Kaveh Edalati,* Hai-Wen Li, Etsuo Akiba, and Zenji Horita

addressed for future applications.[1] Safe 1

4 Magnesium hydride (MgH2) and titanium hydride (TiH2) are two potential and compact storage of hydrogen is among 2
5 candidates for solid-state hydrogen storage, but strong hydride formation the most challenging issues in hydrogen 3
6 energy in these hydrides undesirably results in their high dehydrogenation industry.[2] Hydrogen is mainly stored in 4
the form of high-pressure gas in special 5
7 temperature. First-principles calculations show that the metastable hydrides
tanks, but the price of these tanks is quite 6
8 in the MgH2–TiH2 system have low hydrogen binding energy, which makes high due to the safety issues regarding the 7
9 them more appropriate for low-temperature hydrogen storage. In this study, high-pressure systems.[1,2] Solid-state hy- 8
10 severe plastic deformation (SPD) via the high-pressure torsion (HPT) method drogen storage in the form of metal 9
11 is applied to the MgH2–TiH2 system to synthesize metastable hydrides. While hydrides or complex hydrides provides 10
the most compact method to store hydro- 11
12 MgH2 transforms to a high-pressure orthorhombic γ phase, TiH2 does not
gen under low pressure.[3–5] However, the 12
13 exhibit any cubic-to-tetragonal phase transformation even by HPT processing main drawback of most of the hydrides is 13
14 at cryogenic temperature. Application of large strains by 400 HPT turns to their thermodynamic stability and thus 14
15 the immiscible MgH2/TiH2 composite results in atomic-scale mixing and they need a heating process to release 15
16 formation of nanostructured ternary Mg–Ti–H hydride with the metastable hydrogen.[1–5] 16
17 FCC structure and lower dehydrogenation temperature than TiH2. MgH2 and TiH2 are among the most 17
investigated hydrogen storage materials 18
because of their high hydrogen storage 19
18 capacity such as 7.6 wt% for MgH2 and 20
4.0% for TiH2; however, both MgH2 and 21
19 Dedicated to Professor Terence G. Langdon on TiH2 are thermodynamically stable and release hydrogen at 22
20 the occasion of his 80th anniversary temperatures above 673 K.[5–7] The main strategy used so far to 23
21 destabilize these two hydrides has been chemical modification by 24
addition of other elements.[5–7] For example, it was shown that TiFe 25
and Ti–V–Cr can absorb and desorb hydrogen at ambient 26
22 1. Introduction temperature, but the storage capacity of this hydrides is almost 27
50–75% of TiH2.[8,9] Mg2Ni and Mg4NiPd can absorb and desorb 28
23 Hydrogen is considered as a clean energy carrier, but there are hydrogen at 473 K and room temperature, respectively, but their 29
24 several technical issues regarding the hydrogen production, storage capacity is appreciably lower than that for MgH2.[10,11] 30
25 hydrogen storage, and hydrogen utilization that should be Crystal structure modification is another technique to destabilize 31
hydrides, although the reversibility in this technique is an important 32
Prof. K. Edalati, Prof. K. Kitabayashi, Prof. H.-W. Li, Prof. E. Akiba, issue that should be considered. Metastable hydrides have naturally 33
Prof. Z. Horita smaller formation energy than stable hydrides and thus they can 34
WPI, International Institute for Carbon-Neutral Energy Research
thermodynamically release hydrogen at lower temperatures.[12,13] 35
(WPI-I2CNER)
Kyushu University For example, it was shown that the dehydrogenation temperature of 36
Fukuoka 819-0395, Japan MgH2 can be reduced by 80 K without deteriorating the storage 37
E-mail: kaveh.edalati@kyudai.jp capacity by formation of high-pressure γ phase.[13] 38
Prof. K. Kitabayashi, Prof. K. Edalati, Prof. Z. Horita As shown in Figure 1a, MgH2 has three main crystal 39
Faculty of Engineering structures: α-tetragonal structure which is the most stable phase 40
Department of Materials Science and Engineering
at ambient condition, γ-orthorhombic structure which forms 41
Kyushu University
Fukuoka 819-0395, Japan under 0.39–5.5 GPa and high-pressure β-cubic structure which 42
Prof. H.-W. Li, Prof. E. Akiba forms under 3.9–9.7 GPa.[14,15] TiH2 has two main structures as 43
International Research Center for Hydrogen Energy shown in Figure 1b: cubic FCC which is the most stable phase at 44
Kyushu University ambient condition and tetragonal BCT which forms under high 45
Fukuoka 819-0395, Japan pressures and low temperatures.[16,17] Although Mg and Ti are 46
Prof. H.-W. Li thermodynamically immiscible,[18] there are several reports on 47
Kyushu University Platform of Inter/Transdisciplinary Energy Research the formation of Mg–Ti alloys with the BCC, HCP, and FCC 48
Fukuoka 819-0395, Japan
structures as well as on the formation of Mg–Ti–H hydrides with 49
DOI: 10.1002/adem.201900027 the FCC structure.[19–33] First principles calculations, as shown 50

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High-pressure torsion (HPT) method, which is mainly used 1

as a severe plastic deformation (SPD) technique for grain 2
refinement in metals,[35–37] is a promising process to synthesize 3
metastable phases in different groups of materials.[38] The 4
method has been successfully used by different groups including 5
the group of authors to control the phase transformation in pure 6
metals (Ti,[39,40] Zr,[41,42] Co[43,44]), semiconductor elements 7
(Si,[45,46] Ge,[47,48]), carbon polymorphs (graphite,[44,49] dia- 8
mond,[49] fullerene[50,51]), metallic alloys,[52–56] oxides 9
(Al2O3,[57] ZrO2,[58] BaTiO3,[59] TiO2,[60,61] Y2O3,[62] ZnO,[63] 10
SiO2,[64] VO2,[64]), nitrides (BN,[65]), carbides (SiC[66]), hydrides 11
(MgH2[13,67]), and polymers.[68,69] Moreover, the method has 12
been successfully employed to hydrogen storage materials to 13
enhance the kinetics,[70–72] to improve the activation[73,74] or to 14
synthesize new materials.[75,76] 15
In this study, the HPT is applied to the MgH2–TiH2 system to 16
examine the formation of metastable hydrides. The findings, 17
which report the first application of the HPT method to the 18
hydride/hydride composites, prove the potential of the HPT 19
method for controlling the phase transformations and synthe- 20
sizing metastable hydrides. 21

2. Experimental Section 22

MgH2 and TiH2 powders with 99.8% purity were used for the 23
experiments. The HPT process was conducted on pure MgH2, 24
pure TiH2, and MgH2–50 mol% TiH2 mixture at room 25
temperature under 5 or 6 GPa for N ¼ 0–400 turns at room 26
temperature (T ¼ 300 K) with a rotation speed of ω ¼ 1 rpm. For 27
TiH2, the HPT process was also conducted at cryogenic 28
temperature (T ¼ 77 K) in liquid nitrogen, as attempted in 29
earlier studies on pure metals.[77,78] The samples after HPT 30
processing were in the form of 10 mm diameter discs due to the 31
presence of shallow circular holes on the HPT anvils. 32
The phase transformations in HPT-processed samples were 33
examined by X-ray diffraction (XRD) analysis using the Cu Kα 34
radiation and by Raman spectroscopy using a 532 nm laser. Since a 35
microstructural heterogeneity develops along the disc radii during 36
HPT processing especially when the number of HPT turns is 37
small,[79–81] both XRD and Raman analyses were conducted on 38
regions at 3–5 mm away from the disc center. For MgH2–TiH2 39
composites, the microstructure of sample was examined by 40
transmission electron microscopy (TEM) and the mixing of 41
elements was examined by scanning-transmission electron 42
microscopy (STEM) using an acceleration voltage of 200 kV. Thin 43
foils for STEM and TEM were prepared by crushing the edge part of 44
discs (3–5 mm away from the disc center) in ethanol and depositing 45
Figure 1. Thermodynamic stability of phases in MgH2–TiH2 system. a)
Pressure–temperature phase diagram of MgH2; b) pressure–temperature small amount of crushed samples onto the carbon grids. The 46
phase diagram of TiH2; c) formation enthalpy of cubic and tetragonal microstructural examination by TEM and STEM was conducted by 47
hydrides in MgH2–TiH2 system calculated by first-principles calculations. different modes such as bright-field imaging, dark-field imaging, 48
Data in (a–c) were taken from refs. [13], [15], and [30], respectively. selected-area electron diffraction (SAED) analysis from circular 49
regions with 0.3 mm diameter, high-resolution imaging, fast 50
Fourier transform (FFT) analysis, high-angle annular dark-field 51
1 in Figure 1c, suggested the low stability of high-pressure cubic (HAADF) imaging, and energy dispersive X-ray spectroscopy 52
2 and tetragonal phases in the Mg-rich and Ti-rich sides of the Mg– (EDS). Dehydrogenation of samples was examined by differential 53
3 Ti–H system, respectively.[32,34] However, there has been no scanning calorimetry (DCS) and thermogravimetry (TG) using 54
4 successful attempt to stabilize these phases under ambient 10 mg of samples with a heating rate of 5 K min 1. The samples 55
5 condition. after dehydrogenation test were further examined by XRD analysis. 56

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Figure 3. Formation of FCC hydride in MgH2–TiH2 composite by

straining under high pressure. XRD profiles before and after HPT
processing at room temperature, where (b) is magnified view of (a).

Figure 2. Phase transformations in MgH2 and TiH2 by straining under

high pressure. XRD profiles for (a) MgH2 and (b, c) TiH2 before and after
HPT processing at (a, b) room temperature and (c) cryogenic temperature
in liquid nitrogen.
Figure 4. Strain effect on phase transformations in MgH2–TiH2
composite. Raman spectra before and after HPT processing at room
temperature.

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Figure 5. Strain effect on atomic-scale mixing of elements in MgH2–TiH2 composite. STEM-HAADF micrographs (top) and EDS elemental mapping
with Mg (middle) and Ti (down) for; a) powder mixture and b) sample processed by HPT for 400 turns at room temperature.

1 3. Results HPT processing, while the peaks for the γ phase are not visible 1
in the as-received powder as well as in the sample subjected to 2
2 Phase transformations in pure MgH2 and TiH2 are examined compression without rotation (N ¼ 0). Moreover, the intensity 3
3 using the XRD patterns, as shown in Figure 2. Figure 2a shows of the γ phase peaks increases with increasing the number of 4
4 that MgH2 transforms from the α phase to the γ phase after turns, that is, with increasing the shear strain (γ ¼ 2πrN/h; γ: 5

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Figure 6. Strain effect on grain refinement in MgH2–TiH2 composite. TEM bright-field images (left), dark-field images (right). SAED patterns (center)
and grain size distribution (c) for (a) powder mixture and (b, c) sample processed by HPT for 400 turns at room temperature. Dark-field images were
taken with diffracted beams indicated by arrows in SAED patterns.

1 shear strain; r: distance from disc center, N: number of turns, h: facilitation of phase transformations in metallic and non- 1
2 disc thickness[38]). The current results are consistent with an metallic materials.[39–69] However, as shown in Figure 2b and c, 2
3 earlier publication on HPT processing of MgH2[13] and no phase transformation is detected in TiH2 after HPT 3
4 numerous publications on the effect of shear strain on processing at room and cryogenic temperatures. It is likely 4

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Figure 7. Formation of nanograins with high-missorientation angles in MgH2–TiH2 composite by HPT processing. a) High-resolution image and b, c)
lattice images of regions indicated by B and C in (a), respectively.

1 that the high-pressure tetragonal TiH2 phase forms during the turns. Such a lattice expansion suggests that MgH2 dissolves in 1
2 HPT processing due to the thermodynamic stability of the TiH2 by introducing large plastic strains and a metastable 2
3 phases,[16,17] but it reversely transforms to the FCC phase Mg–Ti–H hydride with the FCC structure is formed. It should be 3
4 shortly after releasing the pressure. noted that in addition to the current ternary Mg–Ti–H FCC 4
5 Phase transformations in the MgH2–TiH2 composite after hydride, ultra-SPD has been successfully employed to synthesize 5
6 HPT processing are shown in XRD patterns of Figure 3 and new hydrogen storage materials in several other immiscible 6
7 Raman spectra of Figure 4. Here, it should be noted that the metallic systems such as Mg–Zr,[83] Mg–Ni–Pd,[11] Mg–V–Cr,[75] 7
8 number of HPT turns were selected as high as 100 and 400 for Mg–Ni–Sn,[82] and some other Mg–V-based alloys.[82] 8
9 this composite because Mg and Ti are thermodynamically Fourth, there is no evidence for the formation of high- 9
10 immiscible[18] and it was shown earlier that the number of turns pressure tetragonal phase by using both XRD analysis and 10
11 for elemental mixing in the immiscible systems should be Raman spectroscopy. Since there is no information about the 11
12 significantly higher than those employed for processing single phase transition pressure in the Mg–Ti–H system, it is hard to 12
13 phase materials (i.e., ultra-SPD should be applied to the comment whether the tetragonal phase is formed during the 13
14 immiscible systems).[54,82] Examination of Figure 3 and 4 HPT processing or it reversely transforms to the FCC phase after 14
15 indicates several main points. releasing the pressure. 15
16 First, MgH2 mainly transforms to a γ phase after HPT Fifth, a significant XRD peak broadening occurs after HPT 16
17 processing for 10 turns, but TiH2 remains stable in the form of processing, indicating that in addition to elemental mixing, 17
18 FCC hydride. Since the FCC hydride does not have any Raman large lattice strain is induced by formation of lattice defects and 18
19 peak, the absence of Raman peaks after HPT processing for 100 decreasing the crystallite size. Details of microstructural 19
20 and 400 turns confirms that the FCC phase is the dominant features are discussed below using electron microscopy 20
21 phase after HPT processing at large strains. techniques. 21
22 Second, after HPT processing for 100 and 400 turns, the peaks The occurrence of elemental mixing after HPT processing is 22
23 of α-MgH2 and γ-MgH2 mainly disappear. However, the peaks shown in STEM-HAADF micrographs and corresponding EDS 23
24 for the FCC phase are clearly visible after processing for various mappings of Figure 5, where Figure 5a corresponds to the 24
25 turns. initial powder mixture and Figure 5b corresponds to the 25
26 Third, as shown in a magnified view of XRD patterns in sample after HPT processing for 400 turns. It is evident that 26
27 Figure 3b, the peaks of FCC phase gradually shift to the lower MgH2 and TiH2 are significantly mixed after HPT processing, 27
28 angles and the lattice parameter increases from 0.445 nm for although Mg-rich and Ti-rich regions are still visible in the 28
29 pure TiH2 powder to 0.449 nm for the sample processed by 400 microstructure. These EDS results are consistent with the 29

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1 XRD analyses in Figure 3. The microstructural features after Dehydrogenation of the MgH2–TiH2 composites after HPT 1
2 HPT processing is shown in TEM dark-field images, bright- processing is shown in Figure 8 using (a) DSC and (b) TG analyses 2
3 field images and SAED patterns of Figure 6, where under an Ar atmosphere. Two peaks are visible in the DSC 3
4 Figure 6a corresponds to the initial powder mixture and analyses: 1) a peak at lower temperatures which corresponds to 4
5 Figure 6b corresponds to the sample processed by HPT for 400 dehydrogenation of MgH2 and Mg-rich regions, and 2) a peak at 5
6 turns. While the initial powders consist of grains with the sizes higher temperature which corresponds to TiH2 and Ti-rich 6
7 mainly at the submicrometer level, the grain sizes significantly regions. The onset of dehydrogenation from MgH2 and Mg-rich 7
8 decrease and reach an average of 13  4 nm after HPT regions can be distinguished in TG analysis, but the onset of 8
9 processing for 400 turns, as shown statistically in Figure 6c. dehydrogenation from TiH2 and Ti-rich regions is not visible 9
10 Such a grain size is much smaller than those reported earlier because the Ti-rich regions desorb hydrogen gradually in a wide 10
11 in HPT-processed metallic materials,[84–86] but are comparable range of temperature. Figure 8 shows that the dehydrogenation 11
12 with the grain sizes of HPT-processed non-metallic oxides.[57– temperature from Mg-rich regions decreases by HPT processing 12
64]
13 The SAED patterns taken from the regions with 300 nm for 10 turns due to the formation of γ phase with lower stability, as 13
14 diameter also show a clear transition to a perfect ring pattern discussed in an earlier publication.[13] However, dehydrogenation 14
15 after HPT processing which indicates that the FCC nanograins from Mg-rich regions occurs at higher temperatures with 15
16 with random missorientations are formed. The formation of increasing the number of turns to 100 and 400 due to the 16
17 FCC nanograins with high missorientation angles is more dissolution of TiH2 in MgH2 and formation of FCC hydride with 17
18 clearly visible in the high-resolution image of Figure 7, where higher stability, in good agreement with Figure 1c. For the Ti-rich 18
19 Figure 7a is a high-resolution image and Figure 7b and c are regions, dissolution of MgH2 in TiH2 by HPT processing reduces 19
20 two lattice images corresponding to the regions B (grain the dehydrogenation temperature which is also consistent with 20
21 interior) and C (grain boundary), respectively. Figure 1c on the effect of Mg dissolution on formation enthalpy of 21
Ti-rich FCC hydrides.[32,34] Examination of samples after DSC-TG 22
analyses using the XRD method, as shown in Figure 9, confirms 23
that hydrogen releases almost fully from both Mg-rich and Ti-rich 24
regions during heating. While the XRD peaks for Mg-rich phase 25
show no peak shift compared to pure Mg, the peaks for Ti-rich 26
phase shift to lower angles compared with pure Ti, suggesting that 27
the Mg partly remains in Ti in the solid solution form due to the 28
slow decomposition kinetics during heating. 29

4. Discussion 30

The thermodynamically stable phases in the M–Ti–H system are 31

pure FCC–TiH2 þ α-MgH2,[32,34] as discussed in Figure 1c. 32
Although the metastable Mg–Ti–H FCC hydrides were already 33
synthesized by ball milling or thin film sputtering,[19–32] this 34
study together with a few earlier publications[11,75,82,83] suggests 35
the potential of ultra-SPD via the HPT processing as an 36

Figure 8. Changes in dehydrogenation by elemental mixing in MgH2–

TiH2 composite. a) Heat flow against temperature achieved by DSC and Figure 9. Decomposition of Mg–Ti FCC hydride to Mg and Ti-rich phase
b) mass loss against temperature achieved by TG before and after HPT by heating. XRD profiles before and after HPT processing at room
processing at room temperature. temperature followed by TG–DSC analyses.

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1 alternative to other mechanochemical processing methods such Conflict of Interest 1

2 as ball milling to produce ternary hydrides even from the
The authors declare no conflict of interest. 2
3 immiscible systems. Since the HPT method introduces shear
4 strain under high pressure, it can synthesize the hydrides within
5 shorter time compared with other mechanochemical synthesis Keywords
6 methods.[87,88] Moreover, a recent study using the neutron high-pressure torsion (HPT), hydrogen storage, metal hydrides, severe
7 diffraction method showed that the Ti-rich Mg–Ti–H hydrides plastic deformation (SPD), ultrafine-grained (UFG) materials
8 synthesized by ball milling consist of the γ-MgH2 clusters in the
3
9 FCC–TiH2 matrix,[33] but the current study confirms that a real Received: January 8, 2019 4
10 atomic-scale mixing and the formation of metastable FCC Mg– Revised: February 12, 2019 5
11 Ti–H hydride occurs by HPT processing. Published online:
12 The main difference between the HPT method and other
13 mechanochemical methods is the introduction of large shear
14 strains under high pressure.[35–38] Application of shear strain [1] A. Zuttel, A. Borgschulte, L. Schlapbach, Hydrogen as a Future Energy 6
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17 Moreover, since large fractions of defects such as vacancies,[89] 34. 9
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