铸态及快淬态CeMg10Ni2合金电化学储氢热力学及动力学性能研究

胡   锋; 罗丽容; 李永治; 翟亭亭; 赵   鑫; 张羊换

doi:10.13208/j.electrochem.180529

电化学 >

2019 , Vol. 25 >Issue 5: 631 - 638

DOI: https://doi.org/10.13208/j.electrochem.180529

研究论文

铸态及快淬态CeMg₁₀Ni₂合金电化学储氢热力学及动力学性能研究

胡锋 ,
罗丽容 ,
李永治 ,
翟亭亭 ,
赵鑫 ,
张羊换

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1. 钢铁研究总院功能材料研究所，北京市海淀区，100081; 2. 内蒙古科技大学材料与冶金学院，内蒙古自治区包头市，014010

收稿日期: 2018-06-27

修回日期: 2018-07-17

网络出版日期: 2018-08-27

基金资助

国家自然科学基金（No. 51761032和51871125）、内蒙古自然科学基金（No.2017BS0507和No. 2018LH05010）、内蒙古科技成果转化项目（No.CGZH2018152）及内蒙古科技大学创新基金项目（No.2014QDL015）

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Investigations in Electrochemical Thermodynamic and Kinetic Properties of As-Cast and As-Quenched CeMg₁₀Ni₂ Hydrogen Storage Alloys

HU Feng ,
LUO Li-rong ,
LI Yong-zhi ,
ZHAI Ting-ting ,
ZHAO Xin ,
ZHANG Yang-huan

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1. Department of Functional Material Research, Central Iron and Steel Research Institute,Beijing 100081, China; 2. The School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, Inner Mongolia, China

Received date: 2018-06-27

Revised date: 2018-07-17

Online published: 2018-08-27

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摘要

为了改善CeMg₁₀Ni₂合金的电化学储氢性能，快淬技术被用来制备具有非晶纳米晶结构的CeMg₁₀Ni₂合金. 运用X射线衍射及高分辨透射电镜对合金的微观结构及其相组成进行分析. 通过恒电流充放电、高倍率放电、交流阻抗以及动电位极化测试对合金的电化学性能进行了详细研究. 研究结果表明，铸态合金由多相结构组成，经过快速凝固处理的合金内部含有大量的非晶纳米晶结构，而且增加的凝固速度可以增强合金内部的非晶纳米晶形成能力. 快速凝固处理减小了合金的热力学参数（ΔH和ΔS），降低了合金氢化物的热稳定性，改善了电化学放电容量. 另外，快速凝固处理显著改善了合金的电化学动力学性能，合金的表观活化能变化进一步解释了这一结论.

关键词： 快速凝固; 非晶纳米晶; 放电容量; 电化学动力学; 活化能

本文引用格式

胡锋 , 罗丽容 , 李永治 , 翟亭亭 , 赵鑫 , 张羊换 . 铸态及快淬态CeMg₁₀Ni₂合金电化学储氢热力学及动力学性能研究[J]. 电化学, 2019 , 25(5) : 631 -638 . DOI: 10.13208/j.electrochem.180529

Abstract

In order to improve the electrochemical hydrogen storage properties of CeMg₁₀Ni₂ alloy, the rapid quenching technology was used to prepare CeMg₁₀Ni₂ alloys with nano-crystalline and amorphous structure. The microstructures of as-cast and as-spinning sample were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical hydrogen storage properties were investigated by an automatic galvanostatic charging/discharging, high rate discharging (HRD), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The results revealed that the as-cast alloy was composed of multiphase structures. The as-quenched alloys were made up of nano-crystalline and/or amorphous structures, and the rapid solidification technology enhanced the glass forming ability of alloys. The rapid spinning technology brought on a reduction in thermodynamic parameters (ΔH and ΔS), which lowered the stability of hydride and ameliorated the discharging capacity of alloy sample. Besides, the as-quenched alloys held better electrochemical kinetics, which may be interpreted by the variation of activation energy.

Key words： rapid solidification; nano-crystalline and/or amorphous; discharging capacity; electrochemistry kinetics; activation energy

参考文献

[1] Jain I P, Lal C, Jain A. Hydrogen storage in Mg: a most promising material[J]. International Journal of Hydrogen Energy, 2010, 35(10): 5133-5144.
[2] Ouyang L Z, Tang J J, Zhao Y J, et al. Express penetration of hydrogen on Mg(10Γ13) along the close-packed-planes[J]. Scientific Reports, 2015, 5(1): 10776-10782.
[3] Kalinichenka S, Röntzsch L, Riedl T, et al. Hydrogen storage properties and microstructure of melt-spun Mg₉₀Ni₈RE₂ (RE = Y, Nd, Gd)[J]. International Journal of Hydrogen Energy, 2011, 36(17): 10808-10815.
[4] Sadhasivam T, Hudso M S L, Pandey S K, et al. Effects of nano size mischmetal and its oxide on improving the hydrogen sorption behaviour of MgH₂[J]. International Journal of Hydrogen Energy, 2013, 38(18): 7353-7362.
[5] Kumar L H, Viswanathan B, Murthy S S. Hydrogen absorption by Mg₂Ni prepared by polyol reduction[J]. Journal of Alloys and Compounds, 2008, 461(1/2): 72-76.
[6] Cheung S, Deng W Q, Duin A C T, et al. ReaxFFMgH reactive rorce rield for magnesium hydride systems[J]. The Journal of Physical Chemistry A, 2005, 109(5): 851-859.
[7] Wang L, Wang X H, Chen L X, et al. Electrode properties of La₂Mg₁₇ alloy ball-milled with x wt.% cobalt powder (x = 50, 100, 150 and 200)[J]. Journal of Alloys and Compounds, 2006, 414(1/2): 248-252.
[8] Chen R G, Wang X H, Ge H W, et al. Effects of surface coating on the electrochemical properties of amorphous CeMg₁₂ composite[J]. Rare Metal Materials and Engineering, 2009, 38(2): 0198-0202
[9] Zhang Y H, Wang H T, Zhai T T. Hydrogen storage performances of LaMg₁₁Ni + xwt% Ni (x=100, 200) alloys prepared by mechanical milling[J]. Journal of Alloys and Compounds, 2015, 645(1): S438-S445.
[10] Hu F, Zhang Y H, Zhang Y, et al. Microstructure and electrochemical hydrogen storage characteristics of CeMg₁₂ + 100wt%Ni + Ywt%TiF₃ (Y=0, 3, 5) alloys prepared by ball milling[J]. Journal of Inorganic Materials, 2013, 28(2): 217-223.
[11] Huang L J, Wang Y X, Tang J G, et al. The study of microstructure and electrochemical properties of Melt-spun Mg-Ni-La alloys[J]. International Journal of Electrochemical Science, 2011, 6(12):6200-6208.
[12] Hu F, Zhang Y, Cai Y, et al. Electrochemical and kinetic study of as-cast and as-quench Mg₂Ni-type hydrogen storage alloys [J]. Journal of Materials Research, 2013, 28(1): 2701-2708.
[13] Wu Y, Lototskyy M V, Solberg J K, et al. Effect of microstructure on the phase composition and hydrogen absorption-desorption behaviour of melt-spun Mg-20Ni-8Mm alloys[J]. International Journal of Hydrogen Energy, 2012, 37(2): 1495-1508.
[14] Lin H J, Ouyang L Z, Wang H, et al. Phase transition and hydrogen storage properties of melt-spun Mg₃LaNi_0.1 alloy [J]. International Journal of Hydrogen Energy, 2012, 37(2): 1145-1150.
[15] Li Y, Li P, Wan Qi, et al. A study of metal hydride as novel thermal energy storage material by using rapid solidification[J]. Journal of Alloys and Compounds, 2016, 689(1): 641-647.
[16] Cheng H H, Yang H G, Li S L, et al. Yang. Effect of hydrogen absorption/desorption cycling on hydrogen storage performance of LaNi_4.25Al_0.75[J]. Journal of Alloys and Compounds, 2008, 453(1/2): 448-452.
[17] Lin H, Ouyang L, Wang H, et al. Hydrogen storage properties of Mg-Ce-Ni nanocomposite induced from amorphous precursor with the highest Mg content[J]. International Journal of Hydrogen Energy, 2012, 37(19): 14329-14335.
[18] Zhang Y H, Li B W, Ren H P, et al. Hydrogen storage behaviours of nanocrystalline and amorphous Mg_20-xLa_xNi₁₀(x=0-6) hydrogen storage alloys[J]. Rare Metal Materials and Engineering, 2010, 39(8): 1317-1322.
[19] Zhang Y H, Zhang W, Gao J L, et al. A comparison study of hydrogen storage thermodynamics and kinetics of YMg₁₁Ni alloy prepared by melt spinning and ball milling[J]. Acta Metallurgica Sinica (English Letters), 2017, 30(11): 1040-1048.
[20] Sakintuna B, Lamari-Darkim F, Hirscher M. Metal hydride materials for solid hydrogen storage: a review[J]. International Journal of Hydrogen Energy, 2007, 32(9): 1121-1140.
[21] Nishina T, Ura H, Uchida S. Determination of chemical diffusion coefficients in metal hydride particals with a microelectrode technique[J]. Journal of The Electrochemical Society, 1997, 144(4): 1273-1278.

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