Recent advances in magnesium-based nanocomposites via in-situ template-confined synthesis

doi:10.11949/0438-1157.20241452

Abstract

Abstract:

Magnesium hydride (MgH₂) is a promising solid-state hydrogen storage material due to its high hydrogen storage capacity (7.6%(mass), 110 kg·m^-3) and low cost. However, its practical application is hindered by its high thermodynamic stability (enthalpy: -74.7 kJ·mol^-1) and slow hydrogen absorption/desorption kinetics. Studies have shown that the in-situ synthesis method successfully achieved the nano-sizing of the Mg/MgH₂ system through a bottom-up assembly strategy, effectively regulating its particle size to improve hydrogen storage performance. This paper reviews the principles behind in-situ synthesis for Mg-based hydrogen storage materials, with a particular focus on methods such as chemical reduction, thermal hydrogenation, and chemical vapour deposition. It also explores how template-confined materials influence the regulation of particle size, hydrogen absorption/desorption kinetics, and the catalytic mechanisms within the Mg/MgH₂ system. Simultaneously, the current challenges in in-situ synthesis techniques are discussed, including high production costs, capacity loss, and poor air stability, while proposing promising strategies for developing high-performance and high-capacity magnesium-based hydrogen storage materials through nanoconfined in-situ fabrication approaches.

Key words: magnesium hydride (MgH₂), solid hydrogen storage, nanoconfined material, desorption, thermodynamics

摘要：

MgH₂作为一种具有高储氢容量［（7.6%（质量分数），110 kg·m^-3］和低成本优势的固态储氢材料，其高热力学稳定性（脱氢焓值-74.7 kJ·mol^-1）及缓慢的吸放氢动力学性能，严重制约了实际应用。研究表明，原位合成法通过自下而上的组装策略，成功实现了Mg/MgH₂体系纳米化，有效调控其粒径从而改善储氢性能。本文综述了化学还原、热氢化、气相沉积等原位合成镁基储氢材料的原理，重点阐述了模板限制材料对Mg/MgH₂体系粒径调节、吸放氢热/动力学性能与催化机理的影响，同时针对当前原位合成技术中存在的制备成本高、容量衰减大及空气稳定性差等挑战进行了探讨，展望了在纳米限域材料作用下原位制备高性能高储量镁基储氢材料的可行方向。

关键词: 氢化镁, 固态储氢, 纳米限域材料, 解吸, 热力学

CLC Number:

TB 34

Jiali WANG, Fang LIU, Wei CHEN, Xiaoying ZHANG, Shengting LI, Tian TIAN, Xiangyu XIN, Guang LIU, Yufei SONG. Recent advances in magnesium-based nanocomposites via in-situ template-confined synthesis[J]. CIESC Journal, 2025, 76(7): 3172-3184.

王佳丽, 刘芳, 陈伟, 张晓英, 李生廷, 田甜, 信翔宇, 刘光, 宋宇飞. 模板限域原位制备镁基纳米复合材料进展[J]. 化工学报, 2025, 76(7): 3172-3184.

Figures/Tables 10

Fig. 1 Kinetic (a) and thermodynamic (b) schematics of magnesium hydride [10]; Improvement principle of kinetics (c) and thermodynamics (d) in hydrogen storage process of magnesium hydride by nanization[11]

Fig.2 Relationship between total energy of MgH2 nanoclusters， Mg nanoclusters and H2 molecular energy and formation energy and particle size[21]

Fig.3 In-situ synthesis methods and nano-confined materials

Fig.4 (a1,a2) TEM images of Mg nanofibers[33]; (a3) SEM image of Mg nanowires prepared from MeMgCl[34]; (b) Diagram of Mg with different morphologies prepared by different synthetic raw materials and end-sealing agents[35]; (c1) SEM image of Mg NPs synthesized in the presence of SDS[35]; (c2) TEM images of Mg nanocrystals with different particle sizes[36]

Fig.5 Schematic diagram and synthesis diagram of high capacity Mg NCs encapsulated by selective permeable polymer[53]

Fig.6 Structure/synthesis diagram and performance diagram of carbon material limited Mg/MgH2

Fig.7 A section schematic diagram of the Mg-TM[68]

Fig.8 Schematic illustration of the fabrication of MgH2@Ti-MX and TPD curves of com-MgH2, hyd-MgBu2 and 60MgH2@Ti-MX[76]

Fig.9 Schematic diagram and performance diagram of MOF and its derivatives nanorestricted Mg/MgH2

Table 1 Hydrogen storage properties of MgH2 limited by different materials （Unless otherwise stated， the initial dehydrogenation temperatures are determined through TPD tests）

材料	制备方法	Mg/MgH₂尺寸/nm	起始脱氢温度/℃	吸放氢焓值ΔH_abs/des/（kJ·mol^-1）	吸放氢活化能E_ab/de/（kJ·mol^-1）	储氢量/%(质量)	文献
HCNs/Mg	化学还原	5~15	—	-65.86/76.73 Bulk：-74.7/74.06	—	4.35	[83]
Fe/Mg	化学还原	3~10(5)	约325(DSC)	ΔH_des = -59.9 ± 1.9	E_de = 137 ± 6	约2.67	[84]
Mg-Ti	化学还原	40~60(50)	约300(DSC)	-73.0 ± 1.8/75.8 ± 4.7	E_de = 50.2	6.2	[85]
Mg-Ni	化学还原	10~20	约244(DSC)	-70.0/70.7	57.4/139.1	6.0	[86]
Mg@Pt	化学还原	3(Pt)	287.5	—	82.4/152.8	6.5	[26]
Mg@Ti@Ni	化学还原	50~600	340(DSC)	-67.12/69.84	E_de = 63.7	6.27	[87]
Mg-Ni-TiS₂	化学还原	70(Mg-Ni)	—	-71.13/72.25	E_ab = 79.4 ± 0.9	约4.7	[25]
Mg/ZIF-67	化学还原	—	约289	-67.5/77.8	E_de = 161.73	5.1	[24]
0.6 MgH₂@CMK-3	浸渍加氢	1~2	50	ΔH_des = 55.4	—	5.5	[56]
MgH₂@BCNTs	浸渍加氢	15~20	220	ΔH_des = 68.92	E_de = 97.97	5.79	[57]
MgH₂@CoS-NBs	浸渍加氢	5~10	约282(DSC)	-65.6/68.1	57.4/120.8	3.23	[82]
Mg@Ni-MOF	浸渍加氢	3	约305(DSC)	-65.7/69.7	41.5/144.7	2.7	[78]
MgH₂/TiO₂	溶剂热法	—	180	—	—	3.4	[70]
MHCH-5	溶剂热法	约5.5	约140	-46.9/49.1	31/43	6.63	[55]
Mg₇₅(TiC_0.6)₁₂@C	气相沉积	<50	—	—	54.7/56.5	5.2	[29]

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