Next Article in Journal
Investigation on the Thermal Effects of WC-Co Turning Inserts Deposited by Additive Manufacturing of Titanium Alloy Powder
Previous Article in Journal
Tribology and Airborne Particle Emission of Laser-Cladded Fe-Based Coatings versus Non-Asbestos Organic and Low-Metallic Brake Materials
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Metals
Volume 11
Issue 11
10.3390/met11111704
metals-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Preparation of Al-3Ga-3In-3Sn Alloy Powder by Coupling Alloying and Ball Milling and Its Application on High-Rate Hydrogen Generation at Room Temperature

by
Shuo Wang
,
Lixiang Zhu
,
Lichen Zhang
,
Xiaodong Zhang
,
Xiaoxuan Wang
,
Mengchen Ge
,
Xiaodong Li
* and
Meishuai Zou
*
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100084, China
*
Authors to whom correspondence should be addressed.
Metals 2021, 11(11), 1704; https://doi.org/10.3390/met11111704
Submission received: 26 September 2021 / Revised: 21 October 2021 / Accepted: 23 October 2021 / Published: 26 October 2021
(This article belongs to the Section Powder Metallurgy)
Browse Figures
Versions Notes

Abstract

:
High hydro-active Al-3Ga-3In-3Sn alloys were prepared by coupling alloying and mechanical milling methods. NiCl2 was added to the alloy during ball milling as the catalyst. XRD, SEM, and XAFS were used for the characterization of the hydro-active alloy. The hydrogen generation properties were systematically investigated in tap water at room temperature. The results show that the hydrogen generation rate is 11.02 L∙min−1∙g−1, and the conversion yield is 90.25% for the Al-3Ga-3In-3Sn-2NiCl2 composite with a ball milling time of 2 h at room temperature in tap water. The hydrolysis reaction contains the expansion of the Al-based phase into a nano-sized layer and the further hydrolysis reaction of the layered Al phase with water. The activation mechanism was also investigated, and the activation of Al was attributed to the Al-Ni galvanic with the existing Cl−, which leads to a faster hydrolysis reaction rate for ball-milled powder with NiCl2.

1. Introduction

Aluminum is an energy storage metal applied in renewable energy cycles [1]. The reaction of Al and water generates high purity hydrogen, Al oxide, and releases a large amount of heat at the same time. The oxidation of Al is renewable, and the heat can be used for the co-generation of heat and power. However, the dense oxide film coating on the Al surface prevented the contact reaction of aluminum and water [2]. Thus, the activation of aluminum is one of the hottest research topics in metal water reactions.
Different methods have been developed to enhance the activation of aluminum and promote the reaction of aluminum and water, such as alloying and mechanical milling. For alloying methods, adding light metals such as Ca [3], Li [4,5], and low-melting-point (LMP) metals such as Ga, In, Sn, Bi and Zn [6,7,8,9,10,11,12,13,14,15,16,17,18] can improve the hydrogen generation reactions of aluminum and water. The activation of aluminum by low melting point alloys is more effective due to the Ga-In-Sn (GIS) phase in Al grains [12,17,19,20]. Various investigations have been performed to enhance the hydrogen generation properties of Al- LMP alloy [10,16,21], and the most effective way is increasing the content of LMP. However, this will decrease the hydrogen generation yield and thus lead to a lower hydrogen storage capacity of the materials. Furthermore, the Al-LMP alloys are always casting blocks or rods; this results in a lower reaction rate at room temperature (not exceeding 200 mL·min−1·g−1) and longer reaction time (can reach 50 min) [6,11,16,19,20,22,23,24,25].
Besides alloying, mechanical milling can effectively activate aluminum by introducing additives such as NaCl [26,27,28,29], KCl [27,28], Fe [30,31,32,33], Co [30,31], Ni [30,31], CoCl2 [31], oxides, hydrides, and other salts [2,34,35,36,37,38]. Recent studies have shown that LMP alloys are also effective in the activation of Al during ball milling. Ternary and quaternary systems show better hydrolysis properties than binary ones [39,40] due to the synergistic effects of LMP. Xiao et al. [39] found the 3 h milled Al-7.5%Bi-2.5%Sn composite exhibits excellent hydrolysis properties. The highest hydrogen conversion yield can reach 86% with a maximum hydrogen generation rate of 570 mL·min−1·g−1 at 35 °C. Wang et al. [40] prolonged the ball milling time to 6 h to further enhance the activation of aluminum. The results show that the hydrogen generation rate of Al-3Ga-3In-5Sn alloy can reach 1560 mL·min−1·g−1 reacting with tap water at room temperature. Although these studies were all focused on the generation rate and amount of hydrogen, few of them reached a hydrogen generation rate high enough for the PEM cell at room temperature (at least 2500 mL·min−1 for 200 W PEM cell considering the auxiliary system).
In this study, we coupled alloying and mechanical milling to combine their advantages to enhance the activation of Al-3Ga-3In-3Sn alloy at room temperature. The solidified Al-3Ga-3In-3Sn alloy powders were taken as the raw material after mechanical disruption for mechanical milling and activation. NiCl2 was added during the ball milling process to study hydrogen production at room temperature.

2. Material and Methods

2.1. Materials

The metals, including Al blocks (99.9% purity), Ga blocks (99.9% purity), In blocks (99.9% purity), and Sn powders (99.9% purity) came from the Shanghai Hutest Laboratory Equipment Co., Ltd. (Shanghai, China), and NiCl2 (analytically pure) is from Alfa Aesar.

2.2. Methods

2.2.1. Alloying and Crushing

Al-3Ga-3Inl-3Sn alloy was made at a designed mass ratio in a resistance furnace at 800 °C for ~2 h. Next, the alloy was directly cast into plates with a thickness of ~100–200 μm by pouring the alloy melt onto a steel plate. The alloy plates were then broken into small powders using mechanical disruption. Finally, the Al-3Ga-3In-3Sn alloy powders and nickel chloride composites were milled for further activation of the aluminum alloy.

2.2.2. Mechanical Ball Milling

The milling experiments were performed using Attritor 01-HD mechanical milling with a chamber volume of 2 L. The Al-3Ga-3In-3Sn (Al-LMP) alloy powders and NiCl2 were weighed according to different ratios in Table 1. The ball-to-powder weight ratio was maintained at 40:1 using stainless steel balls with a diameter of 5 cm. The mixture was milled with a speed of 500 rpm under 0.01 MPa (slightly positive pressure) argon atmosphere.

2.2.3. Characterization

Powder XRD measurements were performed on an X’Pert PRO MPD diffractometer with Cu-Kα radiation. The morphology of the samples was investigated using a Hitachi S4800 microscope electron microscopy (Hitachi High-Tech Corporation, Tokyo, Japan) combined with energy-dispersive X-ray spectroscopy (EDX) for the determination of the metal composition. The Ni K-edge XAFS measurements were performed at the beamline 4B9A of the Beijing Synchrotron Radiation Facility (BSRF) at the Institute of High Energy Physics (IHEP), Chinese Academy of Sciences (CAS) (Beijing, China).

2.2.4. Hydrolysis Reactions

The reactions of metal and tap water at room temperature were performed in the apparatus shown in Figure 1 for hydrogen generation. Here, 0.5 g of the activated composites were used in every experiment. The 0.5 g of active Al-LMP composites were added in a three-neck flask, and 10 mL water was injected with a syringe keeping the water/fuel mass ratio at 20:1. No mixing or heating was done during the reaction process. Hydrogen generation rates were then measured using a mass flow-meter (FS4008, MEMS Technologies) after cooling and condensing to decrease the temperature and eliminate vapor.

3. Results

3.1. Characterization

3.1.1. XRD Analysis

Figure 2 shows the XRD patterns of Al-LMP alloy plates, powders, ball-milled powders, and Al-LMP-NiCl2 composite powders. All samples consist of mainly four phases: Al(Ga) solid solution, InSn4, and In3Sn intermetallic compounds, and a small amount of Al2O3. For Al-LMP alloy plates, Al2O3 (near 23°) and AlO(OH) are detected as the surface oxidation and hydrolyzed of Al. This means the alloy plates had higher activation than that of pure Al. However, only some weak InSn4 and In3Sn intermetallic compound peaks appeared as nonequilibrium solidification during the rapid solidification of Al-LMP alloy plates. In the peaks of InSn4, In3Sn become stronger after mechanical disruption for mechanical milling, which indicates the exposure of these two phases on the samples’ surface. In addition, all the peaks of Al move to a higher degree as the grain refinement after mechanical disruption for mechanical milling. For ball-milled samples without NiCl2, the Al2O3 peaks appeared at near 62° and 67°; however, one extra peak of Al2O3 is detected near 30° for ball-milled powders with NiCl2. This means that the ball-milled Al-LMP-NiCl2 composites are much easier to oxidize. Characteristic peaks of NiCl2 and metal Ni are not detected, which is most likely due to overlapping or low content.

3.1.2. SEM and EDX Analysis

The morphologies of the SEM images of Al-LMP alloy powder are shown in Figure 3. The plates were small with a thickness of ~100–120 μm and were crushed into powder with a diameter no larger than 200 μm with both spherical and small plate shapes. However, all the powders of the samples after ball milling were highly irregular with numerous grain boundaries and plates with sizes no bigger than 200 μm. Increasing the addition of NiCl2 and prolonging the ball milling time can decrease the thickness of the samples.
Figure 4 shows the amplified SEM images of the activated Al-LMP-NiCl2 composites. All powders in the samples were highly irregular plates with numerous grain boundaries and cracks on the particle surface. For the milled Al-LMP in Figure 4a, the surfaces of the powders show a repeat overlying morphology. Moreover, most of the powders were partially oxidized and have irregular globular aggregates on the surface except for the one without the addition of NiCl2, as shown in Figure 4. The EDX analysis revealed that the irregular globular phase was mainly composed of O, Al, and Cl (see in Table 2), and this is consistent with the newly generated Al2O3 detected in XRD. For 1 h ball-milled samples, some Al2O3 powders had cracks (Figure 4c2,d2) while others tended to peel off with fresh alloy surfaces exposed (Figure 4d2,f2). However, for powders after ball milling for over 1 h, linear oxidation was found with irregular globular Al2O3. The EDX data shows high Cl content in Al2O3, as shown in Table 2. This reveals that the Cl−1 (from NiCl2) took part in the oxidation of Al and led to the morphology change of Al2O3. In addition, linear oxidation was observed near the irregular globular oxidation on the surface of the 2 h ball-milled sample.

3.2. Hydrolysis Reactions of the Activated Al-LMP Alloy

3.2.1. Effect of NiCl2 Content

Figure 5 plots the hydrogen evolution and temperature curves for active Al alloy composites with tap water at room temperature. It is clear from Figure 5a,b that the reaction rate is greatly enhanced after ball milling compared with plates and crushing powders. The addition of NiCl2 leads to a significant improvement in the hydrogen generation rate, from ~0.5 L·min−1·g−1 for non-ball-milled samples to over 1.5 L·min−1·g−1 for ball-milled samples. The reaction durations for all ball-milled samples are greatly shortened, from about 2600–1800 s for non-ball-milled samples to about 100 s for 1 h ball-milled samples.
The H2 flow rate patterns are similar for plate sand powders; the hydrogen generation rate (HGR) increases at the early reaction stage and then decreases to a lower value and remains at this level for a long time. The HGR values increase at around 25 min and reach their maximum values of 0.444 L·min−1·g−1 and 0.468 L·min−1·g−1 for plates and powders after over 1400 s. All ball-milled samples exhibit rapid H2 release in the first 20 s with two reaction periods occurring, including the fast initial hydrolysis reaction period and the mild reaction period. The reaction characteristic is different for ball-milled Al-LMP, whether adding NiCl2 or not. For the sample without NiCl2, the first reaction peak occurred at 17.5 s with HGR of 1.798 L·min−1, while the second reaction peak occurred at 38 s with a maximum hydrogen generation rate (MHGR) of 1.956 L·min−1·g−1. However, the intensity of the second reaction period was greatly weakened after ball milling with NiCl2, and the main reaction occurred in the first period with MHGR within 10 s for the hydrolysis reaction of Al-LMP-NiCl2 composites. This change was related to the oxidation on the sample surface, as shown in Figure 4. The oxidation on the sample surface benefited from the fast reaction. The highest hydrogen generation rate was 3.750 L·min−1·g−1 when the content of NiCl2 was 6%. Both the high hydrogen generation rate (1.778 L·min−1·g−1) and hydrogen generation yield (1.046 L·g−1) was achieved when the NiCl2 content was 2%.
The addition of NiCl2 during ball-milling could enhance the hydrogen generation rate, but ball-milling intensifies the oxidation of Al and thus decrease the hydrogen generation yield compared with non-ball-milled samples, as shown in Figure 5c. In addition, the hydrogen generation of the Al/H2O reaction is closely related to temperature. The MHGRs all occur when the temperature has the highest slope, while the highest temperatures are achieved at the highest hydrogen conversion yields according to Figure 5c,d for no further reaction occurred.

3.2.2. Effect of Ball Milling Time

The effect of the ball-milling time on the hydrolysis properties of the Al-LMP-2NiCl2 composite was studied. The hydrogen generation rates and yields of the Al-LMP-2NiCl2 samples reacted with tap water at room temperature were obtained, as shown in Figure 6 and Table 3. In Figure 6a, the HGR increases from less than 2.0 L·min−1·g−1 to over 6.0 L·min−1·g−1 when the ball milling time increases from 1 h to 2 h. The reaction duration was shortened from about ~100 s to only about 30 s for 2–3 h ball-milled composites. The high activity is related to the ball-milling time, which can be confirmed by the linear Al2O3 observed in Figure 4e,f. However, the volume of the hydrogen generation decreases as the milling time increases from 1 h to 3 h; it decreases with prolonged ball milling time and may be the result of surface oxidation. Besides, the hydrolysis reactions of the samples contain only one period, two reaction periods after prolonging the ball milling time to over 2 h. The kinetic characteristics in Table 3 show that both high HGR (11.020 L·min−1·g−1) and HGY (90.25%) are achieved for Al-LMP-2NiCl2 composites after ball milling for 2 h.

3.2.3. The Product of Al-Water Reaction

The XRD patterns of by-products are shown in Figure 7. The results showed that the by-products mainly consist of aluminum AlO(OH) (boehmite), InSn4, and In3Sn, as well as a small amount of Al and Al2O3. The InSn4 and In3Sn do not participate in the hydrolysis reaction; they only act as promoters. The Al peaks were detected due to the imperfect reaction between activated aluminum and tap water. This was consistent with the decrease in conversion yield for active aluminum after ball-milling in Table 3. Al2O3 appeared in the products after the addition of NiCl2 in the Al-LMPM-NiCl2 composite, which can be seen in the SEM images in Figure 4. The intensity of unreacted Al peaks (near 38°, 65°, 78°) increased with the increase of NiCl2. The amount of unreacted Al decreased after prolonging ball-milling time, but unreacted Al still exists.

4. Discussions

4.1. Hydrolysis Reaction Process

To investigate the hydrolysis reaction process and mechanism, intermediate by-products were obtained after the hydrolysis reaction with insufficient water. Figure 8 shows the SEM images of intermediate by-products of Al-LMP plates, powders, and ball milling samples under different conditions. The hydrolysis reaction process for the Al-LMP plates and powders has two steps: The first step is the formation of a layered structure of the Al phase, as seen in Figure 8a1,b1. Similar structures were also reported in the literature [10]. The second step is the Al/H2O reaction, and nano-sized spherical boehmite (~5–10 nm) is formed on the fracture surface of the layer. Due to the low hydrolysis reaction rate of Al-LMP plates and powders, a dense layer of boehmite coating was generated, as shown in Figure 8a3,b2. Thus, the reaction rate declines with the formation of the boehmite coating [26,40].
The intermediate by-products show a different morphology for ball-milled Al-LMP powder, as shown in Figure 8c1. The magnified image of the dark part and gray part in Figure 8c1 are shown in Figure 8c2,c3. Porous spherical nano-boehmite formed with a size of ~20–30 nm on the surface of the layer shown in Figure 8c2. The spherical nano-boehmite generates preferentially in a local position, and a porous structure forms instead of a dense structure. Figure 8c3 shows the final by-product of hydrolysis after a quick hydrolysis reaction. The generation and aggregation of boehmite as dense products lead to the decline of the hydrolysis reaction, and this consists of the hydrogen generation rate shown in Figure 5a,b.
Figure 8d–f shows the reaction processes for ball-milled Al-LMP samples with two NiCl2 for 1–3 h. The morphology of the products changes a lot after the addition of NiCl2. The particle expands with many cracks generated on the surface of 1 h ball-milled powders after partially reacting with water, as shown in Figure 8d1,e1 and f1. The intermediate by-products have two typical morphologies. One is the layered structure of the Al phase similar to Al-LMP alloy plates and powders, as shown in Figure 8d3,e3 and f3. The other one is the loose delaminated final products, as shown in Figure 8d4,e4 and f4 compared with the dense ones in Figure 8c3. It can be noticed that the final product of the Al-LMP-2NiCl2-2h sample is much coarser than others. Besides, the generation of linear production observed in Figure 8e2 indicates the super high local Al activity after the coeffect of prolonging ball-milling and the addition of NiCl2.

4.2. The Effect of Ball-Milling on the Transition of NiCl2

Figure 9a shows normalized Ni K-edge X-ray absorption near-edge structure (XANES) spectra of the Al-LMP-NiCl2 composites as well as the reference samples of Ni foil and NiCl2. The absorption edge (E0) for pure Ni lies at 8333 eV. A higher valence of Ni usually has an absorption edge shifting toward higher energy. Pure NiCl2 features a single peak (A) of the higher intensity and higher absorption edge. It can be observed that the 1 h milled Al-LMP composites powder is more akin to NiCl2. However, the shift of the absorption edge toward low photon energy and the first peak is lower relative to the NiCl2; these changes reveal the negative charge in comparison with the NiCl2, likely because Al is an electron-donor. The XANES curves for 2–3 h milled Al-LMP composite powder changed a lot with the absorption edge shift toward lower photon energy further, as shown in Figure 9a. The obvious energy shift indicates the further electron transfer from the Al atom to the Ni atom after ball-milling for over 2 h. The curves show an intermediate state between metallic Ni and NiCl2. Additionally, the first absorption peak disappeared, and a lower one turned (B) around from 8350 to 8370 eV for Ni in 2 h and 3 h ball-milling powder samples. These obvious changes may cause large changes in the hydrogen generation rates after prolonging the ball-milling time to above 2 h.
Figure 9b shows the Fourier transform of the Ni K-edge EXAFS oscillations in R space (phase-shift correction was not performed). The first nearest-neighbor distance for Ni after ball-milling with the Al-LMP alloy is similar to NiCl2. Two main peaks at the first nearest-neighbor distance were observed. The nearest neighbor distance of the first peak increases compared with NiCl2. However, only one main peak at the first nearest-neighbor distance was even observed in the cases of the 2 and 3 h ball-milled samples. The nearest-neighbor distance of this peak increases compared with NiCl2 and 1 h ball-milled samples. According to this analysis, Ni2+ in NiCl2 was partially reduced after ball-milling with Al-LMP alloy according to both photon energy shift and the Fourier transform of the Ni K-edge EXAFS oscillations in R space in Figure 9b. The results qualitatively indicate the strong influence of ball-milling on the variation in the chemical bonding of the Ni atom in Al-LMP-NiCl2 composites and confirm the exiting of metallic Ni after ball-milling.
Figure 10 shows the morphology of the final products of powders and 1–2 h ball-milled with NiCl2 samples after the hydrolysis reaction with insufficient water. Stacked layer boehmite is observed in Figure 10a1. Nano-sized boehmite powders are generated on the Al layer after the hydrolysis reaction, as shown in Figure 10a2. This dense boehmite layer is a barrier that impedes the reaction of Al and water. However, the morphology of boehmite changes into layers of interwoven lines after ball-milling with NiCl2 for 1 h. The layers shown in Figure 10b2 have a lot of porosities; some layers curl and gradually peel off. After prolonging the ball-milling time further to 2 h, some porous linear boehmite is observed, as shown in Figure 10c1, which formed irregular, fluffy, and linear shapes. Both the layered and fluffy boehmite indicate the higher hydrolysis reaction rate; higher hydrogen flow flushes away the coating boehmite leaving porous boehmite and promoting the Al/H2O reaction in return.

4.3. The Reaction Mechanism of Al-LMP Alloys

The reaction process can be summarized as shown in Figure 11. Firstly, all the samples will expand and turn into layered Al when encountering water, as shown in Figure 11a. This structure change makes it easy for water to get in through the active Al. However, for different samples, the next hydrolysis reaction step varies as the different conditions. For the plates and powders, dense nano-boehmite layers were formed on the surface of layered Al, as shown in Figure 11b. Then the hydrolysis reaction rate declines until thermal accumulation is high enough after a long weak local hydrolysis reaction. Thus, the Al/H2O reaction has a higher H2 rate to break boehmite layers, and the hydrolysis reaction rate increases. The morphology of the boehmite layer becomes porous after ball-milling for 1 h, as shown in Figure 11c. This porous boehmite product leaves more channels for the water to get through and leads to further hydrolysis reactions. The metallic Ni generated after ball milling acts as a cathode in Al-Ni galvanic, which leads to a faster hydrolysis reaction and thus modifies the generated boehmite morphology into a linear form, as shown in Figure 11d. Linear boehmite then forms into a network and peels off from the Al layer surface. It should be noticed that ball-milling time is a key factor in enhancing the hydrolysis reaction rate. On the one hand, the thickness becomes thinner after prolonging the ball-milling time, and a big specific surface area accelerates the reaction rate. On the other hand, the changes, including the transition of NiCl2 into metallic Ni and the following morphology changes of boehmite during the hydrolysis reaction, are attributed to the ball-milling.

5. Conclusions

A series of the active Al-3Ga-3In-3Sn-NiCl2 alloy composites are prepared by coupling alloying and mechanical milling methods. NiCl2 was added to the alloy during ball milling as the catalyst. Low melting point intermetallic phases (In3Sn and InSn4) were exposed, and grain refinement of Al occurred during crushing and ball-milling. Metallic Ni generates after ball-milling NiCl2 with Al-LMP alloy. Metallic Ni acted as the cathode in Al-Ni galvanic, which led to faster corrosion of Al and a high hydrogen release rate for ball-milling powder with NiCl2.
The alloying of Al with low melting point alloy (Ga, In, Sn) can effectively promote the hydrolysis reaction of Al, and the hydrogen generation rate can be further enhanced by ball-milling the Al alloy powders. Increasing the amount of NiCl2 and prolonging the ball-milling time can dramatically increase the hydrogen generation rate of the alloy composites at room temperature, of which was developed to enhance the hydrogen generation properties of Al-3Ga-3In-3Sn alloy at room temperature. Both high hydrogen generation rate (11.020 L·min−1) and conversion yield (90.25%) were achieved for the Al-LMP-2NiCl2 composite after ball-milling for 2 h at room temperature.
The hydrolysis reaction of the Al-LMP alloys and ball-milling composites showed similar processes, including two steps. The expansion of the Al-based phase into the nano-sized layer and the further hydrolysis reaction of the layered Al phase with water. The morphologies of hydrolysis productions varied from dense layer to porous and even linear after prolonged ball-milling. Porous and linear morphology tended to peal off from the surface, and this benefits the further contact reaction of Al and water.

Author Contributions

Conceptualization, M.Z. and S.W.; formal analysis, S.W., L.Z. (Lixiang Zhu), L.Z. (Lichen Zhang), X.Z. and X.W.; funding acquisition, S.W.; project administration, M.Z. and S.W.; writing original draft, S.W.; writing review and editing, S.W., M.G., M.Z. and X.L. All authors have read and agreed to the published version of the manuscript.

Funding

Postdoctoral Research Foundation of China, grant number 2019M660483.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data sharing not applicable.

Acknowledgments

The authors would like to thank the Postdoctoral Research Foundation of China (No. 2019M660483) for financial support; The authors also would like to thank the support given by the beamline scientist, Zhongjun Zheng at beamline 4B9A of the Beijing Synchrotron Radiation Facility (BSRF).

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Ho, T.H.; Pham-Tran, N.-N.; Kawazoe, Y.; Le, H.M. Ab Initio Investigation of O–H Dissociation from the Al–OH2 Complex Using Molecular Dynamics and Neural Network Fitting. J. Phys. Chem. A 2016, 120, 346–355. [Google Scholar] [CrossRef] [PubMed]
  2. Wang, H.-W.; Chung, H.-W.; Teng, H.-T.; Cao, G. Generation of hydrogen from aluminum and water–Effect of metal oxide nanocrystals and water quality. Int. J. Hydrogen Energy 2011, 36, 15136–15144. [Google Scholar] [CrossRef]
  3. Zhao, Z.; Chen, X.; Hao, M. Hydrogen generation by splitting water with Al–Ca alloy. Energy 2011, 36, 2782–2787. [Google Scholar] [CrossRef]
  4. Yang, W.; Zhang, T.; Liu, J.; Wang, Z.; Zhou, J.; Cen, K. Experimental researches on hydrogen generation by aluminum with adding lithium at high temperature. Energy 2015, 93, 451–457. [Google Scholar] [CrossRef]
  5. Chen, X.; Zhao, Z.; Hao, M.; Wang, D. Hydrogen generation by splitting water with Al–Li alloys. Int. J. Energy Res. 2013, 37, 1624–1634. [Google Scholar] [CrossRef]
  6. He, T.T.; Wang, W.; Chen, W.; Chen, D.M.; Yang, K. Influence of In and Sn compositions on the reactivity of Al–Ga–In–Sn alloys with water. Int. J. Hydrogen Energy 2017, 42, 5627–5637. [Google Scholar] [CrossRef]
  7. Xu, S.; Yang, X.-H.; Tang, S.-S.; Liu, J. Liquid metal activated hydrogen production from waste aluminum for power supply and its life cycle assessment. Int. J. Hydrogen Energy 2019, 44, 17505–17514. [Google Scholar] [CrossRef]
  8. Preez, S.P.d.; Bessarabov, D.G. The effects of bismuth and tin on the mechanochemical processing of aluminum-based composites for hydrogen generation purposes. Int. J. Hydrogen Energy 2019, 44, 21896–21912. [Google Scholar] [CrossRef]
  9. Ziebarth, J.T.; Woodall, J.M.; Kramer, R.A.; Choi, G. Liquid phase-enabled reaction of Al–Ga and Al–Ga–In–Sn alloys with water. Int. J. Hydrogen Energy 2011, 36, 5271–5279. [Google Scholar] [CrossRef]
  10. Du, B.; Wang, W.; Chen, W.; Chen, D.; Yang, K. Grain refinement and Al-water reactivity of Al–Ga–In–Sn alloys. Int. J. Hydrogen Energy 2017, 42, 21586–21596. [Google Scholar] [CrossRef]
  11. He, T.; Wang, W.; Chen, D.; Yang, K. Effect of Ti on the microstructure and Al–water reactivity of Al-rich alloy. Int. J. Hydrogen Energy 2014, 39, 684–691. [Google Scholar] [CrossRef]
  12. Wang, W.; Zhao, X.M.; Chen, D.M.; Yang, K. Insight into the reactivity of Al–Ga–In–Sn alloy with water. Int. J. Hydrogen Energy 2012, 37, 2187–2194. [Google Scholar] [CrossRef]
  13. Qiao, D.; Lu, Y.; Tang, Z.; Fan, X.; Wang, T.; Li, T.; Liaw, P.K. The superior hydrogen-generation performance of multi-component Al alloys by the hydrolysis reaction. Int. J. Hydrogen Energy 2019, 44, 3527–3537. [Google Scholar] [CrossRef]
  14. Xie, Z.; Dong, S.; Luo, P.; Wang, H. Enhanced Hydrogen Generation Properties of Al-Ga-In-Sn Alloy in Reaction with Water by Trace Amount of AlTi5B Additives. Mater. Trans. 2017, 58, 724–727. [Google Scholar] [CrossRef] [Green Version]
  15. Lu, J.; Yu, W.; Tan, S.; Wang, L.; Yang, X.; Liu, J. Controlled hydrogen generation using interaction of artificial seawater with aluminum plates activated by liquid Ga–In alloy. RSC Adv. 2017, 7, 30839–30844. [Google Scholar] [CrossRef] [Green Version]
  16. Huang, T.; Gao, Q.; Liu, D.; Xu, S.; Guo, C.; Zou, J.; Wei, C. Preparation of Al-Ga-In-Sn-Bi quinary alloy and its hydrogen production via water splitting. Int. J. Hydrogen Energy 2015, 40, 2354–2362. [Google Scholar] [CrossRef]
  17. Wang, W.; Chen, D.M.; Yang, K. Investigation on microstructure and hydrogen generation performance of Al-rich alloys. Int. J. Hydrogen Energy 2010, 35, 12011–12019. [Google Scholar] [CrossRef]
  18. Wang, W.; Chen, W.; Zhao, X.M.; Chen, D.M.; Yang, K. Effect of composition on the reactivity of Al-rich alloys with water. Int. J. Hydrogen Energy 2012, 37, 18672–18678. [Google Scholar] [CrossRef]
  19. An, Q.; Hu, H.; Li, N.; Liu, D.; Xu, S.; Liu, Z.; Wei, C.; Luo, F.; Xia, M.; Gao, Q. Effects of Bi composition on microstructure and Al-water reactivity of Al-rich alloys with low-In. Int. J. Hydrogen Energy 2018, 43, 10887–10895. [Google Scholar] [CrossRef]
  20. He, T.; Wang, W.; Chen, W.; Chen, D.; Yang, K. Reactivity of Al-rich Alloys with Water Promoted by Liquid Al Grain Boundary Phases. J. Mater. Sci. Technol. 2017, 33, 397–403. [Google Scholar] [CrossRef] [Green Version]
  21. Wang, C.; Liu, Y.; Liu, H.; Yang, T.; Chen, X.; Yang, S.; Liu, X. A Novel Self-Assembling Al-based Composite Powder with High Hydrogen Generation Efficiency. Sci. Rep. 2015, 5, 17428. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  22. Chen, X.; Wang, C.; Liu, Y.; Zou, H.; Lin, K.; Yang, S.; Lu, Y.; Han, J.; Shi, Z.; Liu, X. Portable water-using H2 production materials converted from waste aluminum. Energy Sources Part A 2018, 40, 1991–1997. [Google Scholar] [CrossRef]
  23. Liu, Y.; Liu, X.; Chen, X.; Yang, S.; Wang, C. Hydrogen generation from hydrolysis of activated Al-Bi; Al-Sn powders prepared by gas atomization method. Int. J. Hydrogen Energy 2017, 42, 10943–10951. [Google Scholar] [CrossRef]
  24. Ilyukhina, A.V.; Kravchenko, O.V.; Bulychev, B.M. Studies on microstructure of activated aluminum and its hydrogen generation properties in aluminum/water reaction. J. Alloy Compd. 2017, 690, 321–329. [Google Scholar] [CrossRef]
  25. Mahmoodi, K.; Alinejad, B. Enhancement of hydrogen generation rate in reaction of aluminum with water. Int. J. Hydrogen Energy 2010, 35, 5227–5232. [Google Scholar] [CrossRef]
  26. Czech, E.; Troczynski, T. Hydrogen generation through massive corrosion of deformed aluminum in water. Int. J. Hydrogen Energy 2010, 35, 1029–1037. [Google Scholar] [CrossRef]
  27. Fan, M.Q.; Xu, F.; Sun, L.-X.; Zhao, J.-N.; Jiang, T.; Li, W.-X. Hydrolysis of ball milling Al–Bi–hydride and Al–Bi–salt mixture for hydrogen generation. J. Alloy Compd. 2008, 460, 125–129. [Google Scholar] [CrossRef]
  28. Alinejad, B.; Mahmoodi, K. A novel method for generating hydrogen by hydrolysis of highly activated aluminum nanoparticles in pure water. Int. J. Hydrogen Energy 2009, 34, 7934–7938. [Google Scholar] [CrossRef]
  29. Eom, K.; Cho, E.; Kwon, H. Feasibility of on-board hydrogen production from hydrolysis of Al–Fe alloy for PEMFCs. Int. J. Hydrogen Energy 2011, 36, 12338–12342. [Google Scholar] [CrossRef]
  30. Liang, J.; Gao, L.J.; Miao, N.N.; Chai, Y.J.; Wang, N.; Song, X.Q. Hydrogen generation by reaction of Al–M (M= Fe, Co, Ni) with water. Energy 2016, 113, 282–287. [Google Scholar] [CrossRef]
  31. Eom, K.S.; Kwon, J.Y.; Kim, M.J.; Kwon, H.S. Design of Al–Fe alloys for fast on-board hydrogen production from hydrolysis. J. Mater. Chem. 2011, 21, 13047–13051. [Google Scholar] [CrossRef]
  32. Eom, K.; Kim, M.; Oh, S.; Cho, E.; Kwon, H. Design of ternary Al–Sn–Fe alloy for fast on-board hydrogen production, and its application to PEM fuel cell. Int. J. Hydrogen Energy 2011, 36, 11825–11831. [Google Scholar] [CrossRef]
  33. Fan, M.Q.; Liu, S.; Sun, L.X.; Xu, F.; Wang, S.; Zhang, J.; Mei, D.S.; Huang, F.L.; Zhang, Q.M. Synergistic hydrogen generation from AlLi alloy and solid-state NaBH4 activated by CoCl2 in water for portable fuel cell. Int. J. Hydrogen Energy 2012, 37, 4571–4579. [Google Scholar] [CrossRef]
  34. Deng, Z.Y.; Tang, Y.B.; Zhu, L.L.; Sakka, Y.; Ye, J. Effect of different modification agents on hydrogen-generation by the reaction of Al with water. Int. J. Hydrogen Energy 2010, 35, 9561–9568. [Google Scholar] [CrossRef]
  35. Yang, Y.; Gai, W.Z.; Deng, Z.Y.; Zhou, G.J. Hydrogen generation by the reaction of Al with water promoted by an ultrasonically prepared Al(OH)3 suspension. Int. J. Hydrogen Energy 2014, 39, 18734–18742. [Google Scholar] [CrossRef]
  36. Chen, J.; Xu, F.; Sun, L.; Zhang, K.; Xia, Y.; Guo, X.; Zhang, H.; Yu, F.; Yan, E.; Peng, H.; et al. Effect of doped Ni-Bi-B alloy on hydrogen generation performance of Al-InCl3. J. Energy Chem. 2019, 39, 268–274. [Google Scholar] [CrossRef] [Green Version]
  37. Liu, Y.; Wang, X.; Liu, H.; Dong, Z.; Li, S.; Ge, H.; Yan, M. Improved hydrogen generation from the hydrolysis of aluminum ball milled with hydride. Energy 2014, 72, 421–426. [Google Scholar] [CrossRef]
  38. Xiao, F.; Guo, Y.; Li, J.; Yang, R. Hydrogen generation from hydrolysis of activated aluminum composites in tap water. Energy 2018, 157, 608–614. [Google Scholar] [CrossRef]
  39. Wang, H.; Chang, Y.; Dong, S.; Lei, Z.; Zhu, Q.; Luo, P.; Xie, Z. Investigation on hydrogen production using multicomponent aluminum alloys at mild conditions and its mechanism. Int. J. Hydrogen Energy 2013, 38, 1236–1243. [Google Scholar] [CrossRef]
  40. Fan, M.; Xu, F.; Sun, L. Studies on hydrogen generation characteristics of hydrolysis of the ball milling Al-based materials in pure water. Int. J. Hydrogen Energy 2007, 32, 2809. [Google Scholar]
Metals 11 01704 g001 550
Figure 1. Schematic of the experimental setup for hydrogen generation.
Figure 1. Schematic of the experimental setup for hydrogen generation.
Metals 11 01704 g001
Metals 11 01704 g002 550
Figure 2. XRD patterns of the Al-LMP alloy plates, powders, and Al-LMP-NiCl2 composites.
Figure 2. XRD patterns of the Al-LMP alloy plates, powders, and Al-LMP-NiCl2 composites.
Metals 11 01704 g002
Metals 11 01704 g003 550
Figure 3. SEM images of Al-LMP alloy powder. (a) Plates, (b) crushing powders, (c) 0% NiCl2 (1 h), (d) 2% NiCl2 (1 h), (e) 4% NiCl2 (1 h), (f) 6% NiCl2 (1 h), (g) 2% NiCl2 (2 h), (h) 2% NiCl2 (3 h).
Figure 3. SEM images of Al-LMP alloy powder. (a) Plates, (b) crushing powders, (c) 0% NiCl2 (1 h), (d) 2% NiCl2 (1 h), (e) 4% NiCl2 (1 h), (f) 6% NiCl2 (1 h), (g) 2% NiCl2 (2 h), (h) 2% NiCl2 (3 h).
Metals 11 01704 g003
Metals 11 01704 g004 550
Figure 4. SEM images of active Al-LMP-NiCl2 composites powder (a1) 0% NiCl2 (1 h), (a2) amplified image of a1; (b1) 2% NiCl2 (1 h), (b2) amplified image of b1; (c1) 4% NiCl2 (1 h), (c2) amplified image of c1; (d1) 6% NiCl2 (1 h), (d2) amplified image of d1; (e1) 2% NiCl2 (2 h), (e2) amplified image of e1; (f1) 2% NiCl2 (3 h), (f2) amplified image of f1.
Figure 4. SEM images of active Al-LMP-NiCl2 composites powder (a1) 0% NiCl2 (1 h), (a2) amplified image of a1; (b1) 2% NiCl2 (1 h), (b2) amplified image of b1; (c1) 4% NiCl2 (1 h), (c2) amplified image of c1; (d1) 6% NiCl2 (1 h), (d2) amplified image of d1; (e1) 2% NiCl2 (2 h), (e2) amplified image of e1; (f1) 2% NiCl2 (3 h), (f2) amplified image of f1.
Metals 11 01704 g004
Metals 11 01704 g005 550
Figure 5. The hydrogen generation rate and temperature of Al-LMP-NiCl2 samples with water: (a) hydrogen generation flow rate of plates and powders, (b) hydrogen generation flow rate of ball-milled samples 1–4, (c) hydrogen generation yields, and (d) temperature change during Al/H2O reaction.
Figure 5. The hydrogen generation rate and temperature of Al-LMP-NiCl2 samples with water: (a) hydrogen generation flow rate of plates and powders, (b) hydrogen generation flow rate of ball-milled samples 1–4, (c) hydrogen generation yields, and (d) temperature change during Al/H2O reaction.
Metals 11 01704 g005
Metals 11 01704 g006 550
Figure 6. The hydrolysis reaction between Al-LMP-NiCl2 powders with tap water under different ball milling times: (a) hydrogen generation flow rate, (b) hydrogen generation yields.
Figure 6. The hydrolysis reaction between Al-LMP-NiCl2 powders with tap water under different ball milling times: (a) hydrogen generation flow rate, (b) hydrogen generation yields.
Metals 11 01704 g006
Metals 11 01704 g007 550
Figure 7. XRD patterns of the by-products of Al-LMPM and Al-LMPM composites reacting with tap water.
Figure 7. XRD patterns of the by-products of Al-LMPM and Al-LMPM composites reacting with tap water.
Metals 11 01704 g007
Metals 11 01704 g008 550
Figure 8. SEM images of intermediate by-products of Al-LMP and Al-LMP-NiCl2 ball-milled composites (a1) block, (a2,a3) amplified images of a1; (b1) powders, (b2) amplified image of b1; (c1) 0% NiCl2 (1 h), (c2,c3) amplified images of c1; (d1) 2% NiCl2 (1 h), (d2–d4) amplified images of d1; (e1) 2% NiCl2 (2 h), (e2–e4) amplified images of e1; and (f1) 2% NiCl2 (3 h), (f2–f4) amplified images of f1.
Figure 8. SEM images of intermediate by-products of Al-LMP and Al-LMP-NiCl2 ball-milled composites (a1) block, (a2,a3) amplified images of a1; (b1) powders, (b2) amplified image of b1; (c1) 0% NiCl2 (1 h), (c2,c3) amplified images of c1; (d1) 2% NiCl2 (1 h), (d2–d4) amplified images of d1; (e1) 2% NiCl2 (2 h), (e2–e4) amplified images of e1; and (f1) 2% NiCl2 (3 h), (f2–f4) amplified images of f1.
Metals 11 01704 g008
Metals 11 01704 g009 550
Figure 9. (a) Normalized XANES spectra of Ni K-edge and (b) Fourier-transformed extended X-ray absorption fine structure (EXAFS) of the Al-LMP-2%NiCl2 ball-milled samples for 1–3 h together with NiCl2 and Ni foil.
Figure 9. (a) Normalized XANES spectra of Ni K-edge and (b) Fourier-transformed extended X-ray absorption fine structure (EXAFS) of the Al-LMP-2%NiCl2 ball-milled samples for 1–3 h together with NiCl2 and Ni foil.
Metals 11 01704 g009
Metals 11 01704 g010 550
Figure 10. SEM images of final products of (a1) 0% NiCl2 (1 h), (a2) amplified image of a1; (b1) 2% NiCl2 (1 h), (b2) amplified image of b1; (c1) 2% NiCl2 (2 h), (c2) amplified image of c1.
Figure 10. SEM images of final products of (a1) 0% NiCl2 (1 h), (a2) amplified image of a1; (b1) 2% NiCl2 (1 h), (b2) amplified image of b1; (c1) 2% NiCl2 (2 h), (c2) amplified image of c1.
Metals 11 01704 g010
Metals 11 01704 g011 550
Figure 11. Reaction process for Al-LMP alloys under different conditions. (a) Layered Al reacted with water, (b) plates and powders, (c) ball-milling powders, (d) ball-milling powder with NiCl2.
Figure 11. Reaction process for Al-LMP alloys under different conditions. (a) Layered Al reacted with water, (b) plates and powders, (c) ball-milling powders, (d) ball-milling powder with NiCl2.
Metals 11 01704 g011
Table
Table 1. Composition of Al-LMP-NiCl2 composites.
Table 1. Composition of Al-LMP-NiCl2 composites.
SampleContentAl-Alloy/gNiCl2/gMilling Time/h
1Al-3Ga-3In-3Sn-0NiCl2200.01
2Al-3Ga-3In-3Sn-2NiCl2200.41
3Al-3Ga-3In-3Sn-4NiCl2200.81
4Al-3Ga-3In-3Sn-6NiCl2201.21
5Al-3Ga-3In-3Sn-2NiCl2200.42
6Al-3Ga-3In-3Sn-2NiCl2200.43
Table
Table 2. EDX analysis of ball-milled NiCl2 composites (at.%).
Table 2. EDX analysis of ball-milled NiCl2 composites (at.%).
Sample Area Elements
OAlClNiGaInSn
1111.9985.550.000.001.350.560.56
225.6872.250.000.000.860.630.58
2357.6539.461.310.260.750.320.26
467.7219.6811.860.160.070.300.22
3551.3946.260.920.290.120.630.40
669.7023.694.251.150.060.750.40
4759.1339.670.620.120.220.170.07
868.3824.472.782.551.110.170.54
5971.2619.534.373.750.380.270.43
1072.6623.942.850.240.150.000.00
61162.5228.195.533.020.000.740.01
1278.1317.672.751.280.000.130.04
Table
Table 3. Hydrogen generation properties of the samples with different ball milling parameters.
Table 3. Hydrogen generation properties of the samples with different ball milling parameters.
SampleMilling Time (h)MHGR (mL·min−1)HGY (mL)Conversion Yield (%)
Plates00.480113099.78
Powders00.520112499.25
111.95680671.17
212.450104694.21
312.56286679.53
413.75092688.31
5211.020100290.25
635.74893484.13
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Wang, S.; Zhu, L.; Zhang, L.; Zhang, X.; Wang, X.; Ge, M.; Li, X.; Zou, M. Preparation of Al-3Ga-3In-3Sn Alloy Powder by Coupling Alloying and Ball Milling and Its Application on High-Rate Hydrogen Generation at Room Temperature. Metals 2021, 11, 1704. https://doi.org/10.3390/met11111704

AMA Style

Wang S, Zhu L, Zhang L, Zhang X, Wang X, Ge M, Li X, Zou M. Preparation of Al-3Ga-3In-3Sn Alloy Powder by Coupling Alloying and Ball Milling and Its Application on High-Rate Hydrogen Generation at Room Temperature. Metals. 2021; 11(11):1704. https://doi.org/10.3390/met11111704

Chicago/Turabian Style

Wang, Shuo, Lixiang Zhu, Lichen Zhang, Xiaodong Zhang, Xiaoxuan Wang, Mengchen Ge, Xiaodong Li, and Meishuai Zou. 2021. "Preparation of Al-3Ga-3In-3Sn Alloy Powder by Coupling Alloying and Ball Milling and Its Application on High-Rate Hydrogen Generation at Room Temperature" Metals 11, no. 11: 1704. https://doi.org/10.3390/met11111704

APA Style

Wang, S., Zhu, L., Zhang, L., Zhang, X., Wang, X., Ge, M., Li, X., & Zou, M. (2021). Preparation of Al-3Ga-3In-3Sn Alloy Powder by Coupling Alloying and Ball Milling and Its Application on High-Rate Hydrogen Generation at Room Temperature. Metals, 11(11), 1704. https://doi.org/10.3390/met11111704

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop