过渡金属氟化物改善2NaBH<sub>4</sub>+MgH<sub>2</sub>储氢体系的放氢热力学性能

doi:10.11868/j.issn.1001-4381.2020.000986

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通过机械球磨法制备了2NaBH₄+MgH₂和2NaBH₄+MgH₂+0.1MF_x(M＝Ni，Ti，Zr；x＝2，3，4)储氢复合材料。分别通过扫描电子显微镜(SEM)、能谱分析仪(EDS)和X射线衍射(XRD)分析了复合材料的形貌、元素分布和晶体结构。另外，通过差示扫描量热法(DSC)和程序升温脱附(TPD)测试了材料的放氢热力学性质。结果表明，通过添加NiF₂，TiF₃和ZrF₄，分别将2NaBH₄+MgH₂的第一个放氢峰温降低了8.9，35.7 ℃和54.5 ℃。此外，放氢过程中出现的NaMgF₃相改变了第一个放氢过程的反应路径，并且改变了2NaBH₄+MgH₂的第二次放氢过程，使得第二个脱氢过程的峰温分别降低了18.0，31.1 ℃和34.1 ℃。添加NiF₂，TiF₃和ZrF₄使2NaBH₄+MgH₂的放氢比例分别达到91.7%，91.9%和98.7%。其中ZrF₄对2NaBH₄+MgH₂的整个放氢过程显示出了最好的效果。因此，2NaBH₄+MgH₂+0.1ZrF₄可以作为燃料电池供氢系统的潜在应用体系。

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	郗森良
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	周仕学
	于昊

关键词 ：金属氟化物, 2NaBH₄+MgH₂, 机械球磨法, 热力学稳定性

Abstract：

The 2NaBH₄+MgH₂ and 2NaBH₄+MgH₂+0.1MF_x (M＝Ni, Ti, Zr;x＝2, 3, 4) hydrogen storage composites were prepared by ball milling. The morphology, element distribution, and crystal structure of the composites were detected by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and X-ray diffraction (XRD), respectively. In addition, the hydrogen release thermodynamic properties of the materials were tested by differential scanning calorimetry (DSC) and temperature-programmed desorption (TPD). The results show that the peak temperature of the first hydrogen release process for 2NaBH₄+MgH₂ is decreased by 8.9, 35.7 ℃ and 54.5 ℃ by the addition of NiF₂, TiF₃ and ZrF₄, respectively. In addition, the NaMgF₃ phase that appeared during the hydrogen release process changes the reaction path of the first hydrogen release process, and catalyzes the second hydrogen release process of 2NaBH₄+MgH₂, which reduces the peak temperature of the second dehydrogenation process by 18.0 ℃, 31.1 ℃ and 34.1 ℃, respectively. The quantity ratio of hydrogen release for 2NaBH₄+MgH₂ reaches 91.7%, 91.9% and 98.7% by the addition of NiF₂, TiF₃ and ZrF₄, respectively. In these three catalysts, ZrF₄ shows the best catalytic effect on the entire hydrogen release process of 2NaBH₄+MgH₂. Therefore, 2NaBH₄+MgH₂+0.1ZrF₄can be used as a potential application system of fuel cell hydrogen supply system.

Key words： metal fluoride 2NaBH₄+MgH₂ mechanical ball milling method thermodynamic stability

收稿日期: 2020-10-26 出版日期: 2022-09-20

中图分类号:	TB332
	TK91

基金资助:国家自然科学基金青年项目(21805169);国家自然科学基金面上项目(21978156);山东省自然科学基金(ZR2018BB069);山东省自然科学基金(ZR2018PEM003);山东省高等学校科技计划项目(J17KA113)

通讯作者: 于昊 E-mail: haoyu@sdust.edu.cn

作者简介: 于昊(1983—)，男，副教授，博士研究生，主要研究方向为储氢材料、二氧化碳加氢催化剂制备、生物质转化、精细化学品化学、第一性原理计算等，联系地址：山东省青岛市黄岛区前湾港路579号山东科技大学储能技术学院、化学与生物工程学院(266590)，E-mail: haoyu@sdust.edu.cn

引用本文:

郗森良, 王晓军, 张同环, 韩宗盈, 高猛, 周仕学, 于昊. 过渡金属氟化物改善2NaBH₄+MgH₂储氢体系的放氢热力学性能[J]. 材料工程, 2022, 50(9): 97-104.
Senliang XI, Xiaojun WANG, Tonghuan ZHANG, Zongying HAN, Meng GAO, Shixue ZHOU, Hao YU. Thermodynamic performance of 2NaBH₄+MgH₂ hydrogen storage system improved by transition metal fluoride. Journal of Materials Engineering, 2022, 50(9): 97-104.

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http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2020.000986 或 http://jme.biam.ac.cn/CN/Y2022/V50/I9/97

Fig.1 球磨后2NaBH₄+MgH₂的扫描电镜图(a), (b)和Na(c)，Mg(d)元素分布图

Fig.2 球磨后2NaBH₄+MgH₂+0.1NiF₂的扫描电镜图(a), (b)和Na(c)，Mg(d), Ni(e)元素分布图

Fig.3 球磨后2NaBH₄+MgH₂+0.1TiF₃的扫描电镜图(a), (b)和Na(c)，Mg(d), Ti(e)元素分布图

Fig.4 球磨后2NaBH₄+MgH₂+0.1ZrF₄的扫描电镜图(a), (b)和Na(c)，Mg(d), Zr(e)元素分布图

Fig.5 复合储氢体系球磨后的XRD谱图

Fig.6 复合储氢体系分别升温到450 ℃(a)和600 ℃(b)后的XRD谱图

Fig.7 复合储氢体系在不同升温速率下的DSC曲线

Fig.8 复合储氢体系第一个放氢过程的表观活化能

Fig.9 复合储氢体系在5 ℃/min的升温速率下的TPD曲线

Table 1 不同复合储氢体系的放氢量及放氢质量分数

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