过渡金属氟化物改善2NaBH_(4)+MgH_(2)储氢体系的放氢热力学性能  

Thermodynamic performance of 2NaBH 4+MgH 2 hydrogen storage system improved by transition metal fluoride

作　　者：郗森良 王晓军[1,2] 张同环[1] 韩宗盈[1,2] 高猛 周仕学[1] 于昊[1,2] XI Senliang;WANG Xiaojun;ZHANG Tonghuan;HAN Zongying;GAO Meng;ZHOU Shixue;YU Hao(College of Energy Storage Technology,Shandong University of Science and Technology,Qingdao 266590,Shandong,China;College of Chemical and Biological Engineering,Shandong University of Science and Technology,Qingdao 266590,Shandong,China)

机构地区：[1]山东科技大学储能技术学院,山东青岛266590 [2]山东科技大学化学与生物工程学院,山东青岛266590

出　　处：《材料工程》2022年第9期97-104,共8页Journal of Materials Engineering

基　　金：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,ZR2018PEM003);山东省高等学校科技计划项目(J17KA113)。

摘　　要：通过机械球磨法制备了2NaBH_(4)+MgH_(2)和2NaBH_(4)+MgH_(2)+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NiF_(2),TiF_(3)和ZrF_(4),分别将2NaBH_(4)+MgH_(2)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NaMgF_(3)相改变了第一个放氢过程的反应路径,并且改变了2NaBH_(4)+MgH_(2)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NiF_(2),TiF_(3)和ZrF_(4)使2NaBH_(4)+MgH_(2)的放氢比例分别达到91.7%,91.9%和98.7%。其中ZrF_(4)对2NaBH_(4)+MgH_(2)的整个放氢过程显示出了最好的效果。因此,2NaBH_(4)+MgH_(2)+0.1ZrF_(4)可以作为燃料电池供氢系统的潜在应用体系。The 2NaBH_(4)+MgH_(2)and 2NaBH_(4)+MgH_(2)+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 2NaBH_(4)+MgH_(2)is decreased by 8.9,35.7℃and 54.5℃by the addition of NiF_(2),TiF_(3)and ZrF 4,respectively.In addition,the NaMgF_(3)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 2NaBH_(4)+MgH_(2),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 2NaBH_(4)+MgH_(2)reaches 91.7%,91.9%and 98.7%by the addition of NiF_(2),TiF_(3)and ZrF 4,respectively.In these three catalysts,ZrF_(4) shows the best catalytic effect on the entire hydrogen release process of 2NaBH_(4)+MgH_(2).Therefore,2NaBH_(4)+MgH_(2)+0.1ZrF_(4) can be used as a potential application system of fuel cell hydrogen supply system.

关 键 词：金属氟化物 2NaBH_(4)+MgH_(2) 机械球磨法 热力学稳定性 

分 类 号：TB332[一般工业技术—材料科学与工程] TK91[动力工程及工程热物理]