镁基材料中储氢相及其界面与储氢性能的调控

doi:10.11900/0412.1961.2022.00480

金属学报

2023, Vol. 59

Issue (3): 349-370 DOI: 10.11900/0412.1961.2022.00480

综述

本期目录 | 过刊浏览

镁基材料中储氢相及其界面与储氢性能的调控

李谦¹^,²^,³, 孙璇³, 罗群³, 刘斌³, 吴成章³, 潘复生¹^,²(

)

1 重庆大学国家镁合金材料工程技术研究中心重庆 400044
2 重庆大学材料科学与工程学院重庆 400044
3 上海大学材料科学与工程学院省部共建高品质特殊钢冶金与制备国家重点实验室上海 200444

Regulation of Hydrogen Storage Phase and Its Interface in Magnesium-Based Materials for Hydrogen Storage Performance

LI Qian¹^,²^,³, SUN Xuan³, LUO Qun³, LIU Bin³, WU Chengzhang³, PAN Fusheng¹^,²(

)

1 National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing 400044, China
2 School of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
3 State Key Laboratory of Advanced Special Steel, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China

引用本文:

李谦, 孙璇, 罗群, 刘斌, 吴成章, 潘复生. 镁基材料中储氢相及其界面与储氢性能的调控[J]. 金属学报, 2023, 59(3): 349-370.
Qian LI, Xuan SUN, Qun LUO, Bin LIU, Chengzhang WU, Fusheng PAN. Regulation of Hydrogen Storage Phase and Its Interface in Magnesium-Based Materials for Hydrogen Storage Performance[J]. Acta Metall Sin, 2023, 59(3): 349-370.

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摘要:

镁基储氢材料因储氢密度高、资源丰富、环境友好等优点而备受关注，但其存在吸/放氢温度过高、反应动力学缓慢和循环稳定性差等缺点，阻碍了其大规模产业化进程。尽管镁基储氢材料在新合金体系开发、纳米调控、催化修饰、多相复合等方面取得了巨大进展，但如何获取兼具吸/放氢容量高、温度适中、反应速率快及寿命长等优良性能的镁基储氢材料仍是一个挑战。本文较为系统地总结了镁基材料中储氢相及其界面的种类，论述了其微观组织/界面特征的调控策略和方法。重点探讨了储氢相组成、微观结构及其表/界面结构调控效果对提升储氢热力学与动力学性能的影响规律与作用机制，展望了通过调控储氢相及其界面来设计镁基储氢材料的前景和发展方向。

关键词 ：镁基储氢材料, 储氢相, 表/界面结构, 储氢性能, 调控策略

Abstract：

Mg-based hydrogen storage materials have drawn a lot of attention due to the merit of high hydrogen storage density, earth-abundant resources, and environmental friendliness. However, the slow kinetics, high hydrogen absorption/desorption temperature, and poor cycling stability of Mg-based hydrogen storage materials prevent them from being used on a large scale. The developments of new alloys, nano-structure control, catalytic modification, and multiphase composites, among other things, have made significant progress in Mg-based hydrogen storage materials in recent years. However, challenges still exist, such as high hydrogen storage capacity, moderate adsorption/desorption temperature, rapid reaction rate, and long cycling life. In this review paper, the types of hydrogen storage phases and their interface in Mg-based materials, and the control methods of their microstructure/interface characteristics are systematically summarized. The mechanism of the hydrogen storage phase, microstructure, and surface/interface modifications on the improved thermal/kinetic performance of hydrogen storage are highlighted. This review concludes with an outlook and prospects on the challenge of designing Mg-based hydrogen storage materials by controlling the hydrogen storage phase and the corresponding interface.

Key words： Mg-based hydrogen storage material hydrogen storage phase surface/interface structure hydrogen storage performance regulation strategy

收稿日期: 2022-09-28

ZTFLH:

TG139

基金资助:国家自然科学基金项目(U2102212)

作者简介: 李谦，男，1975年生，教授，博士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2022.00480 或 https://www.ams.org.cn/CN/Y2023/V59/I3/349

Hydrogen	Pearson	Space group	Lattice	Hydride	Hydrogen storage	Ref.
storage	symbol		parameter		capacity
phase			nm		(mass fraction, %)
Mg	hP2	P63/mmc	a = b = 0.32, c = 0.52	MgH₂	7.60	[19]
Mg₂Ni	hP18	P6₂22	a = b = 0.52, c = 1.32	Mg₂NiH₄	3.62	[25]
Mg₂Cu	oF48	Fddd	a = 0.91, b = 1.8,	MgH₂	2.53	[25]
			c = 0.53
Mg₁₇Al₁₂	cI58	$I 4 ¯ 3 m$	bcc a = 1.06	MgH₂	4.40	[19]
Mg₃La	cF16	$F m 3 ¯ m$	bcc a = 0.75	MgH₂, LaH _x (x = 2-3)	2.89	[26]
Mg₁₇La₂	hP38	P63/mmc	a = b = 1.04,	MgH₂, LaH _x (x = 2-3)	4.87	[27,38]
			c =1.02
Mg₁₂Ce	tI26	I4/mmm	a = b = 1.03, c = 0.60	MgH₂, CeH_2.73	5.68	[28]
Mg₃Ce	cF16	$F m 3 ¯ m$	bcc a = 0.74	MgH₂, CeH_2.73	3.62	[28]
Mg₁₂Nd	tI26	I4/mmm	a = b = 1.03, c = 0.59	MgH₂, NdH_2.61	5.63	[29]
Mg₂₄Y₅	cI58	$I 4 ¯ 3 m$	bcc a = 1.13	MgH₂, YH _x (x = 2-3)	5.34	[30]
18R-LPSO (Mg₈₅Zn₆Y₉)	-	C2/m	a = 1.11, b = 1.93,	MgH₂, YH _x (x = 2-3)	4.60-5.30	[31]
18R-LPSO (Mg₈₅Zn₆Y₉)			c = 1.60
18R-LPSO	-	P6₃22	a = b = 0.31, c = 4.86	MgH₂, Mg₂NiH₄, YH _x	4.60	[32]
(Mg₁₂YNi)				(x = 2-3)
14H-LPSO	-	P6₃/mcm	a = b = 1.11, c = 3.66	MgH₂, YH _x (x = 2-3)	5.48	[33]
(Mg₉₂Cu_3.5Y_4.5)
Nd₄Mg₈₀Ni₈	tI92	I4₁/amd	a = b = 1.27, c = 1.59	MgH₂, Mg₂NiH₄, NdH_2.61	4.94	[37]
Nd₁₆Mg₉₆Ni₁₂	oS124	Cmc2₁	a = 1.53, b = 2.17,	MgH₂, Mg₂NiH₄, NdH_2.61	3.92	[36]
			c = 0.95
NdMg₂Ni	oS16	Cmcm	a = 0.41, b = 1.02,	MgH₂, Nd_2.61	2.07	[39]
			c = 0.83
LaMg₂Ni	oS16	Cmcm	a = 0.42, b = 1.03,	LaMg₂NiH₇	1.92	[39]
			c = 0.84
La₂MgNi₉	hR36	$R 3 ¯ m$	a = b = 0.50, c = 2.43	La₂MgNi₉H₁₂	1.60	[40]
LaMgNi₄	cF24	$F 4 ¯ 3 m$	bcc a =0.72	LaMgNi₄H₇	1.40	[41]
2H-La₃MgNi₁₄	-	P6₃/mmc	a = b = 0.50, c = 2.42	La₃MgNi₁₄H₁₈	-	[34]
3R-La₃MgNi₁₄	-	$R 3 ¯ m$	a = b = 0.50, c = 3.61
2H-La₄MgNi₁₉	-	P6₃/mmc	a = b = 0.50, c = 3.23	La₄MgNi₁₉H₂₄	1.50	[35]
3R-La₄MgNi₁₉	-	$R 3 ¯ m$	a = b = 0.50, c = 4.82

表1 不同体系镁基储氢相的晶体结构和储氢容量[19,25~41]

图1 高压扭转(HPT)处理0~1500道次Mg4NiPd的SEM-EDS图，及HPT处理1500道次Mg4NiPd的元素分布、XRD谱和微观组织TEM分析[70]

图2 氢等离子体金属反应(HPMR)法制备的镁基纳米颗粒，磁控溅射制备Mg-Nb合金薄膜，及气相反应合成的Mg纳米线SEM像[21,22,75]

表2 不同调控方法下镁基材料储氢相及组织/界面对比[21,22,56~62,70~73,77~79,81~83]

表3 HPT工艺制备的不同镁基亚稳相[65,67~70]

图3 Mg55Co45合金样品的SEM和TEM像、XRD谱及258 K时Mg55Co45 bcc合金的压力-成分-温度(PCT)曲线[84]

图4 不同纳米结构Mg的吸氢动力学对比[21,75,76,94]

图5 Mg85Ni14Ce1非晶薄膜中F300、F2*250和F10*50样品截面的SEM像和393 K下的放氢动力学[103]

图6 Mg65Ce10Ni20Cu5合金经1、5和10道次HPT工艺前后的XRD谱，熔体快淬和HPT处理1道次后合金的吸氢动力学，及HPT处理1道次后样品的HRTEM像[104]

图7 HPT处理不同转数下Mg样品的OM像、TEM像和SAED花样，及退火样品和经HPT处理0.25和10转数样品的吸氢动力学曲线[66]

图8 HPT处理10道次并在673 K退火后的Mg2Ni样品TEM像和HRTEM分析，有无堆垛层错缺陷的粗晶Mg2Ni的吸氢动力学曲线，及层错缺陷作为氢传输途径的示意图[55]

图9 不同工艺处理纯Mg的EBSD图和相应的极图，不同工艺下纯Mg活化后的吸氢动力学，及熔体快淬(MS)和熔体快淬-冷轧(MS-CR)样品的放氢动力学[52]

图10 5.28%Ni (质量分数)粉末冷喷涂Mg带材后的侧面和表面的形貌及元素分布，423 K、8 × 105 Pa下不同样品的吸氢动力学，及473 K、2 × 104 Pa下不同样品的放氢动力学[111]

图11 累积叠轧(ARB) 30道次Mg-LaNi5-Soot样品TEM明场像(横截面)，累积叠轧5道次Mg-LaNi5-Soot样品横截面TEM明场像，累积叠轧30道次Mg-Soot样品横截面TEM明场像和EDS线扫描叠加的暗场像，及ARB和氢化30 s后Mg-LaNi5-Soot样品横截面微观示意图[115]

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