超晶格La-Mg/Y-Ni复合储氢合金晶体结构及性能研究进展

张晓杰; 田晓; 张颖; 韩家乐; 杨艳春; 塔娜

doi:10.13801/j.cnki.fhclxb.20231017.001

超晶格La-Mg/Y-Ni复合储氢合金晶体结构及性能研究进展

doi: 10.13801/j.cnki.fhclxb.20231017.001

张晓杰¹,
田晓^{1, 2, 3, ,},
张颖¹,
韩家乐¹,
杨艳春¹,
塔娜¹

1.
内蒙古师范大学　物理与电子信息学院，呼和浩特 010022
2.
内蒙古师范大学　稀土功能新能源储能材料内蒙古自治区工程研究中心，呼和浩特 010022
3.
内蒙古师范大学　功能材料物理与化学自治区重点实验室，呼和浩特 010022

基金项目: 内蒙古自治区高等学校碳达峰碳中和研究专项 (STZX202207)；内蒙古自治区科技计划项目(2019GG264；2023YFHH0059)；国家自然科学基金项目(21865021)；内蒙古自然科学基金项目(2021MS05047)

详细信息

通讯作者:
田晓，博士，教授，博士生导师，研究方向为新能源材料、磁性材料　E-mail: nsdtx@126.com

中图分类号: TM911；TB331
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出版历程
- 收稿日期: 2023-07-17
- 修回日期: 2023-09-24
- 录用日期: 2023-10-08
- 网络出版日期: 2023-10-18
- 刊出日期: 2024-03-01

Research progress on crystal structures and properties of superlattice La-Mg/Y-Ni composite hydrogen storage alloys

ZHANG Xiaojie¹,
TIAN Xiao^{1, 2, 3
, ,},
ZHANG Ying¹,
HAN Jiale¹,
YANG Yanchun¹,
TA Na¹

1.
School of Physics and Electronic Information, Inner Mongolia Normal University, Hohhot 010022, China
2.
Inner Mongolia Engineering Research Center of Rare Earth Functional New Energy Storage Materials, Inner Mongolia Normal University, Hohhot 010022, China
3.
Key Laboratory of Physics and Chemistry of Functional Materials, Inner Mongolia Normal University, Hohhot 010022, China

Funds: Carbon Peak Carbon Neutrality Research Project of the Higher Education Institutions of Inner Mongolia Autonomous Region (STZX202207); Science and Technology Plan Project of Inner Mongolia Autonomous Region (2019GG264; 2023YFHH0059); National Natural Science Foundation of China (21865021); Inner Mongolia Natural Science Foundation Project (2021MS05047)

摘要

摘要: 超晶格La-Mg/Y-Ni复合储氢合金具有放电容量大、能量密度高和成本低等优点，是一种重要的氢能存储和转换材料，目前主要用做镍氢电池负极材料和直接硼氢化物燃料电池阳极催化剂。La-Mg-Ni复合合金最初是在La-Ni基储氢合金的基础上，通过用部分Mg替代La而发展起来的。由于La-Mg-Ni复合合金中金属Mg熔点、沸点低，易挥发，导致采用常规熔炼法很难制备；同时合金中的Mg在碱性电解液中容易腐蚀、氧化，导致合金的循环稳定性差。为克服La-Mg-Ni复合合金制备困难和循环稳定性差等问题，研究者又在La-Ni基储氢合金的基础上，通过用部分Y替代La开发出了La-Y-Ni合金。La-Mg-Ni和La-Y-Ni复合合金具有非常相似的超晶格结构，均能表现出很好的储氢性能，均属于同一类新型超晶格结构储氢合金。本文对La-Mg/Y-Ni储氢合金近20多年的研究成果进行了梳理。本文首先介绍超晶格La-Mg-Ni和La-Y-Ni复合合金的相结构组成及相结构的演变规律，同时分析了Mg元素和Y元素部分替代La元素分别对La-Mg/Y-Ni合金结构和性能的影响，然后讨论了La-Mg/Y-Ni复合合金中的相结构对合金性能的影响。最后，指出了超晶格La-Mg/Y-Ni复合储氢合金未来所面临的挑战和发展方向。
- 储氢材料 /
- La-Mg-Ni复合储氢合金 /
- La-Y-Ni复合储氢合金 /
- 相结构 /
- 电化学性能
Abstract: The La-Mg/Y-Ni composite hydrogen storage alloys with superlattice structure have the advantages of large discharge capacity, high energy density and low cost, and are important hydrogen energy storage and conversion material. At present, they are mainly used as the negative material of nickel-metal hydride batteries and anode catalyst of direct borohydride fuel cell. Superlattice La-Mg-Ni composite alloy was originally developed on the basis of La-Ni based hydrogen storage alloy by replacing La with partial Mg. Due to the low melting point and boiling point of Mg and its volatility, La-Mg-Ni alloy is difficult to be prepared by conventional melting method. At the same time, Mg in the alloy is easy to corrode and oxidize in the alkaline electrolyte, resulting in poor cycling stability of the La-Mg-Ni alloy. In order to overcome the difficulties in the preparation and the poor cycle stability of La-Mg-Ni composite alloy, the researchers also developed La-Y-Ni alloy on the basis of La-Ni based hydrogen storage alloy by replacing La with partial Y. La-Mg-Ni and La-Y-Ni alloys have very similar superlattice structures, and both can show good hydrogen storage properties. It can be seen that they belong to the same class of new superlattice structure hydrogen storage alloys. The research achievements of La-Mg/Y-Ni composite hydrogen storage alloys in the past 20 years are reviewed in this paper. The crystal structure and structure evolution of superlattice La-Mg/Y-Ni hydrogen storage alloys are introduced in this paper. Then, the effects of Mg element and Y element partial substitution of La element on the structure and properties of La-Mg/Y-Ni composite alloy are analyzed. At the same time, the effect of phase structures on the properties of La-Mg/Y-Ni composite alloys are discussed. Finally, the future challenges and development directions of superlattice La-Mg/Y-Ni composite hydrogen storage alloys are pointed out.
- hydrogen storage materials /
- La-Mg-Ni composite hydrogen storage alloy /
- La-Y-Ni composite hydrogen storage alloy /
- phase structure /
- electrochemical properties

HTML全文

图 1 AB₅型和AB₂型储氢合金的结构示意图^[10]：(a) CaCu₅；(b) C₁₄；(c) C₁₅

Figure 1. Schematic diagram of structures of AB₅ and AB₂ hydrogen storage alloys^[10]: (a) CaCu₅; (b) C₁₄; (c) C₁₅

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图 2 超晶格La-Mg-Ni和La-Y-Ni复合储氢合金的晶体堆垛结构示意图^[14-15]：(a) La-Mg-Ni；(b) La-Y-Ni

Figure 2. Schematic diagram of crystal structures of superlattice La-Mg-Ni and La-Y-Ni composite alloys^[14-15]: (a) La-Mg-Ni; (b) La-Y-Ni

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表 1 超晶格La-Mg/Y-Ni复合储氢合金的晶体结构

Table 1. Crystal structures of superlattice La-Mg/Y-Ni composite hydrogen storage alloys

Proportion of AB₅ and AB₂	Alloy types	Crystal structures
1∶2	AB₃ type	CeNi₃ type (2H)
		PuNi₃ type (3R)
2∶2	A₂B₇ type	Ce₂Ni₇ type (2H)
		Gd₂Co₇ type (3R)
3∶2	A₅B₁₉ type	Pr₅Co₁₉ type (2H)
		Ce₅Co₁₉ type (3R)

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表 2 La-Mg/Y-Ni复合合金中反应温度条件

Table 2. Reaction temperature conditions in La-Mg/Y-Ni composite alloy

Reaction	LaMgNi₄, LaNi₅ (alloy powders)^[38]	Y₂Ni₄, LaNi₅, La₂YNi₁₅ and La₅Y₄Ni₄₅ (alloy powders)^[15]	La₂MgNi₉ (as-cast)^[39]	La-Ni phase diagram^[39]
Formula (4)	1010-1118 K	1173-1223 K	1073 K	987 K
Formula (6)	1138-1162 K	1353-1383 K	1123 K	1084 K
Formula (8)	1200-1208 K	1415-1435 K	1123 K	1249 K

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表 3 超晶格La-Mg/Y-Ni复合合金常见的晶体学参数

Table 3. Common crystallographic parameters of superlattice La-Mg/Y-Ni composite alloys

Phases and sample	Atoms	Site	x	y	z
PuNi₃-type La₂MgNi₉^[43]	La₁	3a	0	0	0
	La₂	6c	0	0	0.14330
	Mg	6c	0	0	0.14330
	La	3a	0	0	0
PuNi₃-type	Y	3a	0	0	0
Y_0.75La_0.25Ni_3.2Mn_0.3^[44]	La	6c	0	0	0.1418(7)
	Y	6c	0	0	0.1418(7)
2H-Ce₂Ni₇ La_1.5Mg_0.5Ni₇^[45]	La₁	4f	0.33333	0.66667	0.0295(6)
	La₂	4f	0.33333	0.66667	0.0295(6)
	Mg	4f	0.33333	0.66667	0.1710(4)
	La₁	6c	0	0	0.0527(3)
3R-Gd₂Co₇	La₂	6c	0	0	0.0527(3)
La_1.5Mg_0.5Ni₇^[45]	Mg₁	6c	0	0	0.1534(3)
	Mg₂	6c	0	0	0.1534(3)
	La	4f₁	0.33333	0.66667	0.02840
2H-Ce₂Ni₇	Y	4f₂	0.33333	0.66667	0.02840
LaY₂Ni_10.5^[46]	La	4f₁	0.33333	0.66667	0.17367
	Y	4f₂	0.33333	0.66667	0.17367
	La	6c₁	0	0	0.14711
3R-Gd₂Co₇	Y	6c₂	0	0	0.14711
LaY₂Ni_10.5^[46]	La	6c₁	0	0	0.05117
	Y	6c₂	0	0	0.05117
	La	2c₁	0.33333	0.66667	0.25000
2H-Pr₅Co₁₉-type	La	4f₁	0.33333	0.66667	0.1279(5)
La₄MgNi₁₉^[47]	La	4f₂	0.33333	0.66667	0.0194(9)
	Mg	4f₂	0.33333	0.66667	0.0194(9)
	La	2c	0.33333	0.66667	0.25000
	Y	2c	0.33333	0.66667	0.25000
2H-Pr₅Co₁₉	La	4f₁	0.33333	0.66667	0.12942
(La_0.33Y_0.67)₅Ni_17.6Mn_0.9Al_0.5^[48]	Y	4f₁	0.33333	0.66667	0.12942
	La	4f₂	0.33333	0.66667	0.02066
	Y	4f₂	0.33333	0.66667	0.02066

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