Progress in the Research and Application of High-Capacity Mg-Based Hydrogen Storage Alloy Materials

doi:10.11900/0412.1961.2024.00344

Acta Metall Sin

2025, Vol. 61

Issue (3): 420-436 DOI: 10.11900/0412.1961.2024.00344

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Progress in the Research and Application of High-Capacity Mg-Based Hydrogen Storage Alloy Materials

ZOU Jianxin(

), ZHANG Jiaqi, ZHAO Yingyan, LIN Xi, DING Wenjiang

Shanghai Key Laboratory of Hydrogen Science & Center of Hydrogen Science, Shanghai Jiao Tong University, Shanghai 200240, China

Cite this article:

ZOU Jianxin, ZHANG Jiaqi, ZHAO Yingyan, LIN Xi, DING Wenjiang. Progress in the Research and Application of High-Capacity Mg-Based Hydrogen Storage Alloy Materials. Acta Metall Sin, 2025, 61(3): 420-436.

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Abstract

With the rapid advancement of the hydrogen energy industry in recent years, Mg-based solid hydrogen storage materials and their associated storage and transportation systems have garnered significant global attention, leading to numerous groundbreaking studies and remarkable progresses. In the field of material design, high-performance nano Mg-based hydrogen storage materials and modified Mg-based hydrogen storage alloys have significantly enhanced the thermodynamic stability and kinetic properties of Mg and its hydrides. These advancements enable rapid hydrogen absorption and desorption at moderate or even room temperatures, paving the way for cost-effective applications. In terms of system development, the structural design and operational parameters of Mg-based solid hydrogen storage systems have been optimized through advanced simulation techniques and innovative design strategies, thus efficient thermal management of the storage system is achieved. In terms of engineering applications, the world's first ton-level Mg-based solid-state hydrogen storage and transportation trailer has been successfully launched. Additionally, multiple demonstration projects, including Mg-based solid-state hydrogen storage systems and hydrogen refueling stations, have been initiated worldwide. This paper reviews the significant research advancements in Mg-based hydrogen storage materials, focusing on four key areas: nanocrystallization, alloying, system development, and demonstration applications. It also summarizes relevant engineering demonstrations and applications in hydrogen energy storage and transportation, providing suggestions for the future research directions and potential applications.

Key words: hydrogen energy Mg-based hydrogen storage material thermodynamic and kinetic properties numerical simulation Mg-based solid-state hydrogen storage and transportation system

Received: 12 October 2024

ZTFLH:

TK91

Fund: National Natural Science Foundation of China(52201266);National Natural Science Foundation of China(52171186);National Key Research and Development Program of China(2023YFB3809103);Postdoctoral Fellowship Program of CPSF(GZC20231546)

Corresponding Authors: ZOU Jianxin, professor, Tel: (021)54740302, E-mail: zoujx@sjtu.edu.cn

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	ZHANG Jiaqi
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	DING Wenjiang

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https://www.ams.org.cn/EN/10.11900/0412.1961.2024.00344 OR https://www.ams.org.cn/EN/Y2025/V61/I3/420

Fig.1 Solid-state hydrogen storage materials and their volume/weight hydrogen density indicators released by the US Department of Energy (DOE)^[2] (CNT—carbon nanotube)

Fig.2 MgH₂-Ni@NCS nanocomposite hydrogen storage material prepared by HCS + HEBM^[21] (Ni@NCS—nano-nickel particle coated nitrogen-doped carbon sphere, HCS—hydriding combustion synthesis, HEBM—high-energy ball-milling; T_m—peak temperature, E_a—activation energy, R²—goodness of fit; % refers to the mass percentage in this paper)
(a) process flow (b) SEM spherical morphologies
(c) dehydrogenation performance (d) cycle stability

Fig.3 Mechanism diagram of nano-confined MgH₂/Ni@pCNF^[32] (pCNF—porous carbon nanofiber)

Fig.4 Preparation schematic and TEM characterization of non-confined ultrafine MgH₂^[33] (THF—tetrahydrofuran)

Fig.5 Preparation process and performance diagrams of Mg-Ga alloy^[38]

Fig.6 Mechanism diagram of hydrogen sorption in Mg₉₅Y₃Zn₂ alloy^[41]

Fig.7 Morphologies and hydrogen storage performance mechanism diagrams of Mg-Ni-Gd-Y-Zn-Cu alloy^[43]

Fig.8 Typical TEM results of Mg₉₃Y₃Zn₂Al₂ alloy^[44]
(a) Y₃Zn₃Al₄ phase
(b) interface between Y₃Zn₃Al₄ phase and Mg matrix
(c) SAED of Y₃Zn₃Al₄ phase
(d) EDS mapping of Y₃Zn₃Al₄ phase
(e) Al₂Y phase (f, g) interface between Al₂Y phase and Mg matrix (h) SAED of Al₂Y phase

Fig.9 Intermetallic phase transition from MgIn to Mg₃In (a) and in situ XRD spectra during dedeuteration in Mg-In-D system (b)^[45]

Fig.10 Effect of heat transfer oil flow rate (u_f) on average reaction fraction of magnesium-nickel alloys hydrogen storage tanks (a) and reaction fraction distributions on cross-section with average reaction fraction of 0.8 (b-f)^[52]

Fig.11 PID diagram of potential applications for coupling hydrogen directly heated Mg-based hydrogen storage tanks (HST) with SOEC and SOFC^[53] (PID—process & instrumentation drawing, SOEC—solid oxide electrolysis cell, SOFC—solid oxide fuel cell)

Fig.12 Schematics of the traditional structure (a, c) and sandwich structure (b, d) of a Mg-based solid hydrogen storage system coupled with phase change materials^[59] (R1-R4—radii of different interlayers)
(a, b) top views (c, d) axial views

Fig.13 Mg-based solid hydrogen storage material developed by McPhy company (a) and Mg-based solid state hydrogen storage device (b)^[60] (CPM—phase changing material, MGH—external reaction heat management)

Fig.14 The world's first ton-level magnesium-based solid hydrogen storage and transportation device (a), the second generation tank-type ton-level magnesium-based solid hydrogen storage device (b), and ton-level magnesium-based solid hydrogen storage and hydrogen refueling station (c)^[61]

Fig.15 Applications of Mg-based solid state hydrogen storage and transportation technology in different industrial fields

1	Schlapbach L, Züttel A. Hydrogen-storage materials for mobile applications [J]. Nature, 2001, 414: 353
2	Guan D Q, Wang B W, Zhang J G, et al. Hydrogen society: From present to future [J]. Energy Environ. Sci., 2023, 16: 4926
3	Møller K T, Jensen T R, Akiba E, et al. Hydrogen—A sustainable energy carrier [J]. Prog. Nat. Sci.: Mater. Int., 2017, 27: 34
4	Yue M L, Lambert H, Pahon E, et al. Hydrogen energy systems: A critical review of technologies, applications, trends and challenges [J]. Renew. Sustain. Energy Rev., 2021, 146: 111180
5	Hassan I A, Ramadan H S, Saleh M A, et al. Hydrogen storage technologies for stationary and mobile applications: Review, analysis and perspectives [J]. Renew. Sustain. Energy Rev., 2021, 149: 111311
6	Han G, Lu Y F, Jia H X, et al. Magnesium-based energy materials: Progress, challenges, and perspectives [J]. J. Magnes. Alloy., 2023, 11: 3896
7	Ren L, Li Y H, Zhang N, et al. Nanostructuring of Mg-based hydrogen storage materials: Recent advances for promoting key applications [J]. Nano-Micro Lett., 2023, 15: 93 doi: 10.1007/s40820-023-01041-5 pmid: 37037950
8	Zhao Y Y, Wang B L, Ren L, et al. Nanostructured MXene-based materials for boosting hydrogen sorption properties of Mg/MgH₂ [J]. Mater. Rep.: Energy, 2024, 4: 100255
9	Yang Y X, Zhang X, Zhang L C, et al. Recent advances in catalyst-modified Mg-based hydrogen storage materials [J]. J. Mater. Sci. Technol., 2023, 163: 182 doi: 10.1016/j.jmst.2023.03.063
10	Zhang X L, Liu Y F, Zhang X, et al. Empowering hydrogen storage performance of MgH₂ by nanoengineering and nanocatalysis [J]. Mater. Today Nano, 2020, 9: 100064
11	Zhang J Q, Hou Q H, Guo X T, et al. Achieve high-efficiency hydrogen storage of MgH₂ catalyzed by nanosheets CoMoO₄ and rGO [J]. J. Alloys Compd., 2022, 911: 165153
12	Hou Q H, Zhang J Q, Guo X T, et al. Improved MgH₂ kinetics and cyclic stability by fibrous spherical NiMoO₄ and rGO [J]. J. Taiwan Inst. Chem. Eng., 2022, 134: 104311
13	Zhao Y Y, Zhu Y F, Shi R, et al. Structural inhomogeneity: A potential strategy to improve the hydrogen storage performance of metal hydrides [J]. J. Mater. Chem., 2023, 11A: 13255
14	Li Q, Lu Y F, Luo Q, et al. Thermodynamics and kinetics of hydriding and dehydriding reactions in Mg-based hydrogen storage materials [J]. J. Magnes. Alloy., 2021, 9: 1922
15	Aguey-Zinsou K F, Ares-Fernández J R. Hydrogen in magnesium: New perspectives toward functional stores [J]. Energy Environ. Sci., 2010, 3: 526
16	Wagemans R W P, van Lenthe J H, de Jongh P E, et al. Hydrogen storage in magnesium clusters: Quantum chemical study [J]. J. Am. Chem. Soc., 2005, 127: 16675 pmid: 16305257
17	Varin R A, Czujko T, Wronski Z. Particle size, grain size and γ-MgH₂ effects on the desorption properties of nanocrystalline commercial magnesium hydride processed by controlled mechanical milling [J]. Nanotechnology, 2006, 17: 3856
18	Huang S J, Mose M P. High-energy ball milling-induced crystallographic structure changes of AZ61-Mg alloy for improved hydrogen storage [J]. J. Energy Storage, 2023, 68: 107773
19	Lang C G, Ouyang L Z, Yang L L, et al. Enhanced hydrogen storage kinetics in Mg@FLG composite synthesized by plasma assisted milling [J]. Int. J. Hydrogen Energy, 2018, 43: 17346
20	Zou R, Zhang W J, Dai M, et al. One-step synthesis of light metal nanoparticle from metastable complex [J]. Small, 2023, 19: 2206518
21	Wang Y, Ding Z M, Li X J, et al. Improved hydrogen storage properties of MgH₂ by nickel@nitrogen-doped carbon spheres [J]. Dalton Trans., 2020, 49: 3495 doi: 10.1039/d0dt00025f pmid: 32104875
22	Ren L, Zhu W, Li Y H, et al. Oxygen vacancy-rich 2D TiO₂ nanosheets: A bridge toward high stability and rapid hydrogen storage kinetics of nano-confined MgH₂ [J]. Nano-Micro Lett., 2022, 14: 144 doi: 10.1007/s40820-022-00891-9 pmid: 35838926
23	Ren L, Li Y H, Li Z, et al. Boosting hydrogen storage performance of MgH₂ by oxygen vacancy-rich H-V₂O₅ nanosheet as an excited H-pump [J]. Nano-Micro Lett., 2024, 16: 160 doi: 10.1007/s40820-024-01375-8 pmid: 38512500
24	Zhao Y Y, Liu Z B, Liu J C, et al. Improvement effect of reversible solid solutions Mg₂Ni(Cu)/Mg₂Ni(Cu)H₄ on hydrogen storage performance of MgH₂ [J]. J. Magnes. Alloy., 2024, 12: 197
25	Zhu C Y, Hosokai S, Akiyama T. Growth mechanism for the controlled synthesis of MgH₂/Mg crystals via a vapor-solid process [J]. Cryst. Growth Des., 2011, 11: 4166
26	Zhao Y Y, Zhu Y F, Shi R, et al. Magnesium nickel hydride monocrystalline nanoparticles for reversible hydrogen storage [J]. Mater. Rep.: Energy, 2024, 4: 100246
27	Pantić T, Mamula B P, Soderžnik K Ž, et al. The influence of defects on hydrogen sorption from Mg-V thin films [J]. Int. J. Hydrogen Energy, 2024, 54: 457
28	Li W Y, Li C S, Ma H, et al. Magnesium nanowires: Enhanced kinetics for hydrogen absorption and desorption [J]. J. Am. Chem. Soc., 2007, 129: 6710 pmid: 17488082
29	Norberg N S, Arthur T S, Fredrick S J, et al. Size-dependent hydrogen storage properties of Mg nanocrystals prepared from solution [J]. J. Am. Chem. Soc., 2011, 133: 10679 doi: 10.1021/ja201791y pmid: 21671640
30	Liu W, Aguey-Zinsou K F. Hydrogen storage properties of in-situ stabilised magnesium nanoparticles generated by electroless reduction with alkali metals [J]. Int. J. Hydrogen Energy, 2015, 40: 16948
31	Lu C, Ma Y L, Li F, et al. Visualization of fast “hydrogen pump” in core-shell nanostructured Mg@Pt through hydrogen-stabilized Mg₃Pt [J]. J. Mater. Chem., 2019, 7A: 14629
32	Ren L, Zhu W, Zhang Q Y, et al. MgH₂ confinement in MOF-derived N-doped porous carbon nanofibers for enhanced hydrogen storage [J]. Chem. Eng. J., 2022, 434: 134701
33	Zhang X, Liu Y F, Ren Z H, et al. Realizing 6.7 wt% reversible storage of hydrogen at ambient temperature with non-confined ultrafine magnesium hydrides [J]. Energy Environ. Sci., 2021, 14: 2302
34	Liang C X, Wang Z B, Zhang M J, et al. Research progress on magnesium-based solid hydrogen storage nanomaterials [J]. Energy Storage Sci. Technol., 2024, 13: 788
	梁宸曦, 王振斌, 张明锦等. 镁基固态储氢材料的研究进展 [J]. 储能科学与技术, 2024, 13: 788 doi: 10.19799/j.cnki.2095-4239.2023.0826
35	Reilly J J, Wiswall R H. Reaction of hydrogen with alloys of magnesium and copper [J]. Inorg. Chem., 1967, 6: 2220
36	Reilly J J, Wiswall R H. Reaction of hydrogen with alloys of magnesium and nickel and the formation of Mg₂NiH₄ [J]. Inorg. Chem., 1968, 7: 2254
37	Zou J X, Ding W J. Review of research hotspots in magnesium-based hydrogen storage materials in 2023 [J]. Sci. Technol. Rev., 2024, 42(1): 204 doi: 10.3981/j.issn.1000-7857.2024.01.013
	邹建新, 丁文江. 2023年镁基储氢材料研究热点回眸 [J]. 科技导报, 2024, 42(1): 204 doi: 10.3981/j.issn.1000-7857.2024.01.013
38	Zhang B W, Zeng Z Q, Li J C, et al. Microstructure and hydrogen storage properties of magnesium-gallium binary alloys [J]. J. Phys. Chem. Solids, 2024, 190: 112028
39	Zhang J X, Ding X, Chen R R, et al. Effective attempt towards enhancing hydrogen storage performance of LPSO phase contained high-capacity Mg-based alloy by Indium [J]. Int. J. Hydrogen Energy, 2024, 50: 431
40	Lu Y S, Wang H, Liu J W, et al. Reversible de/hydriding reactions between two new Mg-In-Ni compounds with improved thermodynamics and kinetics [J]. J. Phys. Chem., 2015, 119C: 26858
41	Zhang J X, Ding X, Chen R R, et al. Precursor H-induced pyrolysis towards hydrogen storage properties enhancement of Mg-Y-Zn alloys with diverse Y level [J]. J. Power Sources, 2023, 560: 232695
42	Tan X F, Kim M, Gu Q F, et al. Na-modified cast hypo-eutectic Mg-Mg₂Si alloys for solid-state hydrogen storage [J]. J. Power Sources, 2022, 538: 231538
43	Yao H, Zeng G, Tan X F, et al. Hydrogen storage performance and phase transformations in as-cast and extruded Mg-Ni-Gd-Y-Zn-Cu alloys [J]. J. Mater. Sci. Technol., 2023, 151: 162 doi: 10.1016/j.jmst.2022.12.015
44	Zhang J X, Ding X, Chen R R, et al. Diversification of interfaces triggered hydrogen storage properties enhancement [J]. Rare Met., 2024, 43: 2324
45	Ma Z W, Huang Z Y, Li Z, et al. Insights into thermodynamic destabilization in Mg-In-D hydrogen storage system: A combined synchrotron X-ray and neutron diffraction study [J]. Energy Storage Mater., 2023, 56: 432
46	de Brito Ferraz M, Botta W J, Zepon G. Synthesis, characterization and first hydrogen absorption/desorption of the Mg₃₅Al₁₅Ti₂₅-V₁₀Zn₁₅ high entropy alloy [J]. Int. J. Hydrogen Energy, 2022, 47: 22881
47	El Osery I A. Theory of the computer code RET 1 for the calculation of space-time dependent temperature and composition properties of metal hydride hydrogen storage beds [J]. Int. J. Hydrogen Energy, 1983, 8: 191
48	Lucas G, Richards W. Mathematical modelling of hydrogen storage systems [J]. Int. J. Hydrogen Energy, 1984, 9: 225
49	Nasako K, Ito Y, Hiro N, et al. Stress on a reaction vessel by the swelling of a hydrogen absorbing alloy [J]. J. Alloys Compd., 1998, 264: 271
50	Jemni A, Nasrallah S B. Study of two-dimensional heat and mass transfer during desorption in a metal-hydrogen reactor [J]. Int. J. Hydrogen Energy, 1995, 20: 881
51	Mat M D, Kaplan Y, Aldas K. Investigation of three‐dimensional heat and mass transfer in a metal hydride reactor [J]. Int. J. Energy Res., 2002, 26: 973
52	Lin X, Yin C L, Ren L, et al. A one- and three-dimensional coupled model and simulation investigation for the large-scale oil-heating type Mg-based hydrogen storage tank [J]. Chem. Eng. J., 2023, 472: 144943
53	Shao L F, Lin X, Bian L S, et al. Engineering control strategy of hydrogen gas direct-heating type Mg-based solid state hydrogen storage tanks: A simulation investigation [J]. Appl. Energy, 2024, 375: 124134
54	Wu Z, Yang F S, Zhang Z X, et al. Magnesium based metal hydride reactor incorporating helical coil heat exchanger: Simulation study and optimal design [J]. Appl. Energy, 2014, 130: 712
55	Wu Z, Yang F S, Zhu L Y, et al. Improvement in hydrogen desorption performances of magnesium based metal hydride reactor by incorporating helical coil heat exchanger [J]. Int. J. Hydrogen Energy, 2016, 41: 16108
56	Nyamsi N S, Wu Z, Zhang Z X, et al. Dehydrogenation performance of metal hydride container utilising MgH₂-based composite [J]. Appl. Therm. Eng., 2022, 209: 118314
57	Ye Y, Lu J F, Ding J, et al. Performance improvement of metal hydride hydrogen storage tanks by using phase change materials [J]. Appl. Energy, 2022, 320: 119290
58	Lutz M, Bhouri M, Linder M, et al. Adiabatic magnesium hydride system for hydrogen storage based on thermochemical heat storage: Numerical analysis of the dehydrogenation [J]. Appl. Energy, 2019, 236: 1034
59	Chang H, Tao Y B, Ye H. Numerical study on hydrogen and thermal storage performance of a sandwich reaction bed filled with metal hydride and thermochemical material [J]. Int. J. Hydrogen Energy, 2023, 48: 20006
60	Jehan M, Fruchart D. McPhy-Energy's proposal for solid state hydrogen storage materials and systems [J]. J. Alloys Compd., 2013, 580: S343
61	Ren L, Li Y H, Lin X, et al. Promoting hydrogen industry with high-capacity Mg-based solid-state hydrogen storage materials and systems [J]. Front. Energy, 2023, 17: 320 doi: 10.1007/s11708-023-0889-1

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