储氢合金中氢致非晶化的研究进展

doi:10.11896/cldb.19050189

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Abstract Hydrogen storage alloys are considered to be a kind of good hydrogen storage medium, and their high hydrogen absorption and desorption capacity during cycling is the focus of research. However, their capacity degradation is unavoidable. The main degradation mechanisms are alloy particle pulverization, electrochemical corrosion and oxidation, and hydrogen-induced amorphization (HIA), in which HIA occurs in the AB₂ type alloy hydride containing Laves phase or AB_3-3.8 type rare earth nickel alloy hydrides containing Lave phase subunits.
The factors affecting the occurrence of HIA are mainly hydrogen concentration, hydrogen pressure, temperature, number of cycles, and phase type. When the hydrogen concentration is low,HIA occurs in a part of alloy hydride after hydrogen absorption. The degree of HIA increases with the increase of hydrogen concentration. Whether the HIA occurs is completely related to the critical value of hydrogen pressure and temperature. When the value is over the critical value, HIA phenomenon is getting severe, when the value is lower than the critical value, the crystals coexist with the crystalline hydride. As the increase of cycling number, the HIA phenomenon is getting severe, which directly reduces the hydrogen desorption efficiency of the alloy.
Phase tuning has been proved that can improve the hydrogen absorption and desorption properties of the alloy. Mg, Pr, Sm and Co, Mn, Cu, Fe and Al are applied to partly replace RE and Ni in the RENi₂ (RE=rare earth) alloy, respectively. HIA inevitably occurs when the formed alloys absorb hydrogen, nevertheless, their hydrogen absorption and desorption properties of the alloy have been improved. The analyzed results show that after partial substitution of elements, the alloy phase transforms from a single AB₂ type structure to the coexistence phases of AB₂ type Laves phase and CaCu₅ type AB₅ phase. HIA occurs after hydrogen absorptionin AB₂ phase, while AB₅ phase is always crystalline. With the increase of cycling numbers, the HIA rate of the alloy is different when Ni is partly replaced by Fe, Mn and Si. For the phases containing AB₂ unit or AB₂ subunit, the sequence of HIA occurrence from easy to difficult is (La, Mg)Ni₂> (La, Mg)Ni₃> (La, Mg)₂Ni₇> (La, Mg)₅Ni₁₉. In order to delay or inhibit HIA, appropriate replacement of alloy elements, increasing the proportion or content of AB₅ structural layer and recrystallization of alloy hydride may be investigated.
In this paper, the research progress of HIA during hydrogen absorption is summarized in the alloy containing AB₂ unit or AB₂ subunit. The necessary conditions, influencing factors, phenomena and causes for HIA occurrence are introduced respectively. The delay measures of HIA are put forward and their prospects are forecasted, aiming to provide references for the development of hydrogen storage alloys with long life and high capacity.

Key words： hydrogen storage alloy metal hydride AB₂ structure unit hydrogen-induced amorphization

Published: 14 July 2020

CLC number:

TG139.1

Fund:This work was financially supported by the National Natural Science Foundation of China(51371094), National Science Foundation of Hebei Province, China, (E2018201235), Hebei University Laboratory Opening Project 2018 (sy201811).

About author:: Xiaoping Dong, associate professor, master tutor, doctor, Department of Mechanical Design, Manufacturing and Automation, Hebei University. He mainly engaged in investigation of the composition design and perfor-mance regulation of hydrogen storage materials. He has participated and completed over ten projects, including National Natural Science Foundation, Hebei Natural Science Foundation. He has published over 50 papers and 2 invention patents in domestic and foreign journals about hydrogen storage materials. Among them, 30 SCI/EI articles were included. In 2015, He obtained the third prize of the 6th Young Teachers' Classroom Teaching Competition of Hebei University, and was awarded as an
excellent reviewer of the Journal of Materials Heat Treatment. He was selected as a member of the Inner Mongolia Nanotechnology Standardization Committee (SAM/TC) in 2018.

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Cite this article:

DONG Xiaoping,CHEN Yafang,SU Jianwen, et al. Research Progress on Hydrogen-induced Amorphization in Hydrogen Storage Alloys[J]. Materials Reports, 2020, 34(15): 15110-15115.

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http://www.mater-rep.com/EN/10.11896/cldb.19050189 OR http://www.mater-rep.com/EN/Y2020/V34/I15/15110

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