添加C10H10Cl2Ti对6LiBH4-CaH2-3MgH2体系储氢性能的影响  

Effect of C10H10Cl2Ti on Hydrogen Storage Properties of 6LiBH4-CaH2-3MgH2 System

作　　者：饶崇顺 张欣[2] 杨敬豪 刘倩 周轶凡 RAO Chong-Shun;ZHANG Xin;YANG Jing-Hao;LIU Qian;ZHOU Yi-Fan(Henan Key Laboratory of Advanced Magnesium Alloy,School of Materials Science and Engineering,Zhengzhou University,Zhengzhou 450001,China;State Key Laboratory of Silicon Materials,School of Materials Science and Engineering,Zhejiang University,Hangzhou 310027,China;Teaching and Research Office,PLA Army Academy of Artillery and Air Defense(Zhengzhou Campus),Zhengzhou 450000,China)

机构地区：[1]河南省先进镁合金重点实验室,郑州大学材料科学与工程学院,郑州450001 [2]硅材料国家重点实验室,浙江省电池新材料及应用技术重点实验室,浙江大学材料科学与工程学院,杭州310027 [3]中国人民解放军陆军炮兵防空兵学院郑州校区教学科研处,郑州450000

出　　处：《无机化学学报》2019年第12期2233-2242,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.U1504525);河南省高等学校重点科研项目计划(No.15A430050)资助

摘　　要：C10H10Cl2Ti的添加可以有效改善6LiBH4-CaH2-3MgH2样品吸放氢性能,添加的质量分数为5%时具有较好的催化效果。样品的起始和终止放氢温度比原始样品分别降低约30和25℃,可逆储氢量(质量分数)约为8.1%。添加C10H10Cl2Ti催化剂的样品在360℃下等温放氢速率比原始样品提高了178%。两步放氢反应的表观活化能分别为131.4和138.8 kJ·mol^-1,相比原始样品降低了约18.6%和15.8%。利用X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)对样品进行分析发现,热分解过程中C10H10Cl2Ti生成了多价态的Ti化合物,催化了LiBH4与CaH2的反应,从而改善了复合体系的储氢性能。C10H10Cl2Ti was selected as an additive to improve the hydrogen storage properties of the 6LiBH4-CaH2-3MgH2 sample,with optimum hydrogen storage performances by 5%(w/w)addition.The onset and ending temperatures for the dehydrogenation of the sample were 30 and 25℃,which were lower than those of the pristine sample,and its reversible hydrogen storage capacity was about 8.1%(w/w).The desorption rate of the C10H10Cl2Ti-doped sample was 1.78 times faster than that of the pristine sample in the isothermal dehydrogenation mode at 360℃.The apparent activation energy(Ea)of the two-step reaction was calculated to be 131.4 and 138.8 kJ·mol^-1,which were 18.6%and 15.8%lower than the pristine sample,respectively.Further XPS analyses indicate that the multivalence state Ti compounds generate during thermal decomposition of C10H10Cl2Ti,which plays an important role to improve the hydrogen storage properties of the 6LiBH4-CaH2-3MgH2 system.

关 键 词：储氢材料 C10H10Cl2Ti LiBH4 吸放氢性能 动力学 

分 类 号：TB33[一般工业技术—材料科学与工程]