原位电阻测试分析Mg(BH4)2制备MgB2的成相过程

果辰; 蔡欣炜; 罗文浩; 黄子耕; 冯庆荣; 甘子钊

doi:10.7498/aps.70.20210620

摘要

Mg(BH₄)₂作为优质的储氢材料, 在约300 ℃开始分解释放H₂, 并最终生成MgB₂. 由于Mg(BH₄)₂的释氢反应可以在较低的温度下获得MgB₂, 使其成为了制备MgB₂超导材料的一种有效途径. 本文采用了原位电阻法, 通过测量Mg(BH₄)₂分解过程中电阻温度曲线, 详细地研究了Mg(BH₄)₂分解生成MgB₂的相变过程. 同时, 利用电阻温度的微分曲线, 确定了在分解过程中不同产物的成相温度(T_PF). 其中, MgB₂的成相温度可以低至410 ℃. 通过与粉末烧结法制备MgB₂块材的成相温度对比, 估算出反应前Mg的颗粒尺寸最低可达3.4 nm. 此外, 样品的XRD分析给出了生成的MgB₂晶粒在10—18 nm之间, 在SEM图像中也同样观察到了MgB₂纳米纤维结构. 这表明, Mg(BH₄)₂分解生成的Mg与B 形成了接近原子级的混合, 从而使MgB₂可以在更低的成相温度(410 ℃)、更短的反应时间内成相. 该方法为MgB₂在超导应用的制备提供了新的思路, 有利于实现MgB₂的工业化生产.

关键词:

MgB₂ /
Mg(BH₄)₂ /
原位电阻法

Abstract

Mg(BH₄)₂ was previously studied as a promising hydrogen storage material, because of its high gravimetric storage capacities for hydrogen and suitable thermodynamic properties. Mg(BH₄)₂ began to decompose at about 300 ℃, and formed MgB₂ at the end of hydrogen desorption process with the weight content of 14.9% of hydrogen lost. Aside from the prominent hydrogen storage property, the decomposition process from Mg(BH₄)₂ to MgB₂ can be a potential method for fabricating superconducting MgB₂ at a low sintering temperature. In this paper, MgB₂ bulk was prepared by an in-situ reaction, using the Mg(BH₄)₂ pressed block as a precursor. The resistance change of the sample was monitored during the Mg(BH₄)₂ decomposition process and the resistance-temperature (R-T) curve of this process was recorded. Phase of MgH₂, Mg and B were formed as the block slowly release its hydrogen before MgB₂ occurred. According to the R-T curve, the phase formation of MgB₂ started in a relatively low temperature of 410 ℃. Because MgB₂ was critically formed by Mg and B derived from Mg(BH₄)₂, we can compare our formation temperature with previous study on MgB₂ prepared by Mg and B in different particle size. The fitting result indicated that the particle size of Mg and B harvest from Mg(BH₄)₂ decomposition was only 3.4 nm on average. The nearly atomic level mixture of Mg and B resulted in a high chemical reactivity, which was the main reason for low sintering temperature. X-ray diffraction results showed that the purity of MgB₂ was 95.2%, and the size of MgB₂ grains was 10–18 nm. SEM images showed that the MgB₂ bulk had a porous structure and poor connectivity, which was caused by large amount the hydrogen release during the decomposition. MgB₂ nanofibers can also be observed inside the bulk. In the superconductivity test, the superconducting transition temperature of the bulk was 35 K. After all, such in situ method to fabricate MgB₂ showed a great advantage in some aspects, as its low-cost precursors, low sintering temperature, small grain-size and high superconducting transition temperature in the formed MgB₂, which have the potential in industrial scale fabrication of MgB₂ bulks and wires.

Keywords:

作者及机构信息

北京大学物理学院, 人工微结构和介观物理国家重点实验室, 北京　100871

通信作者: 蔡欣炜, xwcai@pku.edu.cn

Authors and contacts

State Key Laboratory for Artificial Microstructure and Mesoscopic Physics, Department of Physics, Peking University, Beijing 100871, China

Corresponding author: Cai Xin-Wei, xwcai@pku.edu.cn

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参考文献

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[8]	Yang J, Zheng J, Zhang X Z, Li Y Q, Yang R, Feng Q R, Li X G 2010 Chem. Commun. 46 7530 Google Scholar
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[15]	Zhuang C G, Liu X X, Guo T, Wang B, Li X G, Chen C P, Feng Q R 2007 Supercond. Sci. Technol. 20 1125 Google Scholar
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施引文献

图 1 Mg(BH₄)₂原位烧结制备的MgB₂块材

Fig. 1. MgB₂ bulk fabricated by in situ reaction from Mg(BH₄)₂

下载: 全尺寸图片幻灯片

图 2 Mg(BH₄)₂原位烧结的电阻温度曲线及微分曲线

Fig. 2. R-T curve and differential curve for in situ reaction from Mg(BH₄)₂.

下载: 全尺寸图片幻灯片

图 3 成相温度与Mg颗粒度之间的拟合曲线

Fig. 3. Fitting curve of Mg particle size dependence of phase forming temperature.

下载: 全尺寸图片幻灯片

图 4 Mg(BH₄)₂原位烧结制备的MgB₂的XRD衍射图

Fig. 4. XRD diffraction pattern of MgB₂ fabricated by in situ reaction from Mg(BH₄)₂.

下载: 全尺寸图片幻灯片

图 5 50 Oe下MgB₂样品的抗磁性曲线, 插图为超导转变温度(T_C)附近的放大曲线

Fig. 5. M-T curve of the MgB₂ sample measured under 50 Oe, the inset shows the enlarged curve near T_C.

下载: 全尺寸图片幻灯片

图 6 Mg(BH₄)₂制备的MgB₂的SEM图像　(a) MgB₂块材的整体形貌; (b) Mg(BH₄)₂制备出的MgB₂纳米纤维; (c) MgB₂纳米纤维生长形成的MgB₂晶块

Fig. 6. SEM image of MgB₂ fabricated by Mg(BH₄)₂: (a) The morphology of the MgB₂ bulk; (b) MgB₂ nanofibers generated from Mg(BH₄)₂; (c) MgB₂ grains formed by MgB₂ nanofibers.

下载: 全尺寸图片幻灯片

表 1 不同颗粒度Mg粉对应的MgB₂成相温度

Table 1. Phase forming temperature of MgB₂ fabricated by different sized Mg powders.

样品编号 1 2 3 4

T_PF/K 908 876 842 727
a/μm 100 45 15 0.04

下载: 导出CSV

map

[1]	Nakamori Y, Miwa K, Ninomiya A, Li H, Ohba N, Towata S I, Zuettel A, Orimo S I 2006 Phys. Rev. B 74 045126 Google Scholar
[2]	Voss J, Hummelshøj J S, Łodziana Z, Vegge T 2008 J. Phys.: Condens. Matter 21 012203 Google Scholar
[3]	Li H W, Kikuchi K, Nakamori Y, Ohba N, Miwa K, Towata S, Orimo S 2008 Acta Mater. 56 1342 Google Scholar
[4]	Chlopek K, Frommen C, Leon A, Zabara O, Fichtner M 2007 J. Mater. Chem. 17 3496 Google Scholar
[5]	Fujii H, Ozawa K 2011 Supercond. Sci. Technol. 24 095009 Google Scholar
[6]	Luo W H, Huang Z G, Cai X W, Niu R R, Nie R J, Feng Q R, Wang F R, Gan Z Z 2019 Supercond. Sci. Technol. 32 085006 Google Scholar
[7]	Yang J Z, Zhang X Z, Zheng J, Song P, Li X G 2010 Scripta Mater. 64 225 Google Scholar
[8]	Yang J, Zheng J, Zhang X Z, Li Y Q, Yang R, Feng Q R, Li X G 2010 Chem. Commun. 46 7530 Google Scholar
[9]	Chen L P, Zhang C, Wang Y B, Wang Y, Feng Q R, Gan Z Z, Yang J Z, Li X G 2010 Supercond. Sci. Technol. 24 015002 Google Scholar
[10]	张辰, 陈丽萍, 王银博, 吴桃李, 刘文静, 刘雨潇, 薛驰, 冯庆荣 2011 低温 33 97 Google Scholar Zhang C, Chen L P, Wang Y B, Wu T L, Liu W J, Liu Y X, Xue C, Feng Q R 2011 Chin. J. Low Temp. Phys. 33 97 Google Scholar
[11]	郭峥山, 陈艺灵, 冯庆荣 2012 真空科学与技术学报 32 693 Google Scholar Guo Z S, Chen Y L, Feng Q R 2012 J. Vac. Sci. Technol. 32 693 Google Scholar
[12]	Chen Y L, Liao X B, Cai X Q, Yang C, Guo Z S, Niu R R, Zhang Y, Jia C Y, Feng Q R 2017 Physica C 542 34 Google Scholar
[13]	Guo C, Wang H Z, Cai X W, Luo W H, Huang Z G, Zhang Y, Feng Q R, Gan Z Z 2021 Physica C 584 1353863 Google Scholar
[14]	Hanada N, Chopek K, Frommen C, Lohstroh W, Fichtner M 2008 J. Mater. Chem. 18 2611 Google Scholar
[15]	Zhuang C G, Liu X X, Guo T, Wang B, Li X G, Chen C P, Feng Q R 2007 Supercond. Sci. Technol. 20 1125 Google Scholar
[16]	Chen C P, Zhou Z J, Li X G, Xu J, Wang Y H, Gao Z X, Feng Q R 2004 Solid State Commun. 131 275 Google Scholar
[17]	DeFouw J D, Quintana J P, Dunand D C 2008 Acta Mater. 56 1680 Google Scholar
[18]	冯庆荣, 陈晋平, 徐军, 王宇昊, 陈鑫 2004 低温 26 46 Google Scholar Feng Q R, Chen C P, Xu J, Wang Y H, Chen X 2004 Chin. J. Low Temp. Phys. 26 46 Google Scholar
[19]	Yamamoto A, Shimoyama J-i, Ueda S, Katsura Y, Horii S, Kishio K 2004 Supercond. Sci. Technol. 18 116 Google Scholar
[20]	Yamamoto A, Shimoyama J, Ueda S, Katsura Y, Iwayama I, Horii S, Kishio K 2006 Physica C 445-448 806 Google Scholar

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原位电阻测试分析Mg(BH₄)₂制备MgB₂的成相过程