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Mg-Nb及Mg-Nb2O5復(fù)合儲氫材料粉體的制備及其性能
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上海市科委基礎(chǔ)研究重點項目(10JC1407700);上海市自然科學(xué)基金(11ZR1417600); 教委創(chuàng)新重點項目(12ZZ017); 重大專項(10DZ2211000);上海市浦江人才計劃項目(11PJ1406000)


Synthesis and Properties of Mg-Nb and Mg-Nb2O5 Composite Hydrogen Storage Powders
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    摘要:

    采用直流電弧等離子體法結(jié)合原位鈍化法制備Mg-Nb和 Mg-Nb2O5復(fù)合儲氫材料超細粉體,并利用ICP、XRD、TEM、P-C-T、TG-DTA等測試手段研究對比粉體的成分、相組成、微觀形貌、顆粒粒徑和吸放氫性能。ICP分析顯示Mg-Nb粉中Nb含量高于Mg-Nb2O5粉,但均低于初始含量。XRD和TEM皆在Mg-Nb粉中發(fā)現(xiàn)MgNb2O3.67相,而Mg-Nb2O5中有NbO2.46新相生成。Mg-Nb粉的P-C-T曲線吸放氫平臺更平坦,滯后更??;計算出Mg-Nb粉的氫化生成焓為–73.33 kJ/mol H2,低于Mg-Nb2O5粉的–82.45 kJ/mol H2。氫化后粉體的TG-DTA分析,Mg-Nb粉的放氫峰更尖銳,放氫速度更快。Mg-Nb粉體更佳的熱力學(xué)和動力學(xué)性能證明鈍化引入的氧化物MgNb2O3.67起到了催化作用,而Mg-Nb2O5中的NbO2.46由于含量少、分布不均勻等原因催化效果差。以上結(jié)果證明經(jīng)過鈍化獲得氧化物的催化效果好于直接電弧蒸發(fā)

    Abstract:

    The Mg-Nb and Mg-Nb2O5 hydrogen storage composite powders were prepared through arc plasma method followed by in-situ passivation. The composition, the phase component, the morphology, the particle size and the hydrogen storage properties of two powders were systematically analyzed by using inductive coupled plasma emission spectrometer (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM), pressure-composition-temperature (PCT) and thermogravimetry/differential thermal analysis (TG/DTA) techniques. ICP analyses reveal that the Nb contents of both powders reduce compared with their initial compositions. In addition, Nb content in Mg-Nb powder is higher than that in Mg-Nb2O5 powder. XRD results show that MgNb2O3.67 phase exists in Mg-Nb powder and NbO2.46 phase in Mg-Nb2O5 powder. TEM observations reveal that the MgNb2O3.67 particles are distributed more homogeneously and their particle sizes are smaller than those of the NbO2.46 particles in Mg-Nb2O5 powder. PCT analyses show that the hydrogen sorption plateaus of the Mg-Nb powder are wider and smoother with a smaller absorption/desorption gap compared to those of Mg-Nb2O5 powder. Based on Van’t Hoff equation, the hydrogenation enthalpy of the Mg-Nb powder is determined to be –73.33 kJ/mol H2, lower than the value of –82.45 kJ/mol H2 for Mg-Nb2O5 powder. TG-DTA measurements show that the hydrogenated Mg-Nb powder has a faster desorption rate and a sharper endothermic desorption peak compared to those of the hydrogenated Mg-Nb2O5 powder. The better hydrogen storage thermodynamic and kinetic properties of Mg-Nb powder may be attributed to the catalytic effect of MgNb2O3.67 generated in passivation. In contrast, the NbO2.46 phase can be reduced during hydrogenaing. Also, it has a low content and a heterogeneous distribution in Mg-Nb2O5 powder and thus possesses a poor catalytic effect. The above results show that the arc plasma method followed by in-situ passivation is an more efficient approach to produce metal-oxide hydrogen storage composite with a superior catalytic effect of oxide compared with the directly evaporated oxide

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郭 皓,鄒建新,曾小勤,丁文江. Mg-Nb及Mg-Nb2O5復(fù)合儲氫材料粉體的制備及其性能[J].稀有金屬材料與工程,2013,42(11):2404~2409.[Guo Hao, Zou Jianxin, Zeng Xiaoqin, Ding Wenjiang. Synthesis and Properties of Mg-Nb and Mg-Nb2O5 Composite Hydrogen Storage Powders[J]. Rare Metal Materials and Engineering,2013,42(11):2404~2409.]
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  • 收稿日期:2012-11-15
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