Destabilization of LiBH4 dehydrogenation through H+-H- interactions by cooperating with alkali metal hydroxides

被引:20
作者
Cai, Weitong [1 ,2 ]
Wang, Hui [1 ,2 ]
Sun, Dalin [3 ]
Zhang, Qingan [4 ]
Yao, Xiangdong [5 ]
Zhu, Min [1 ,2 ]
机构
[1] S China Univ Technol, Sch Mat Sci & Engn, Guangzhou 510640, Guangdong, Peoples R China
[2] Key Lab Adv Energy Storage Mat Guangdong Prov, Guangzhou 510640, Guangdong, Peoples R China
[3] Fudan Univ, Dept Mat Sci, Shanghai 200433, Peoples R China
[4] Anhui Univ Technol, Sch Mat Sci & Engn, Maanshan 243002, Anhui, Peoples R China
[5] Griffith Univ, Queensland Micro & Nanotechnol Ctr, Nathan, Qld 4111, Australia
基金
中国国家自然科学基金;
关键词
HYDROGEN STORAGE PROPERTIES; BOROHYDRIDES; STABILITY; DECOMPOSITION; REVERSIBILITY; SYSTEM; MGH2; LI;
D O I
10.1039/c3ra45847d
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Destabilization by the alkali metal hydroxides LiOH, NaOH, and KOH in the solid-state dehydrogenation of LiBH4 is reported. 6.5 wt% of hydrogen was liberated within 10 minutes at 250 degrees C. Destabilization originated from the interaction between H+ in [OH](-) and H- in [BH4](-). A larger Pauling's electronegativity of the alkali metal (Li > Na > K) led to a greater acidity of the proton donor [OH](-) site, and thus enhanced destabilization. The temperature of the predominant dehydrogenation was reduced to 207, 221, and 230 degrees C, for ball milled LiBH4-LiOH, 2LiBH(4)-NaOH, and 2LiBH(4)-KOH, respectively. The LiBH4: LiOH stoichiometry greatly affected the destabilization, by providing differing reaction pathways in LiBH4-xLiOH (x = 1, 1.36, 4). The incremental increase in the LiOH content of LiBH4-xLiOH increased the dehydrogenation rate, but the temperature increased from 207 degrees C (x = 1) to 250 degrees C (x = 4). 4.1 and 6.5 wt% of hydrogen was liberated within 10 minutes by LiBH4-LiOH and LiBH4-4LiOH, respectively. The incremental increase in dehydrogenation temperature was attributed to differing [BH4](-)center dot center dot center dot/[OH](-) interactions, formed by the differing stoichiometric ratios.
引用
收藏
页码:3082 / 3089
页数:8
相关论文
共 42 条
[1]   Stability and Reversibility of Lithium Borohydrides Doped by Metal Halides and Hydrides [J].
Au, Ming ;
Jurgensen, Arthur R. ;
Spencer, William A. ;
Anton, Donald L. ;
Pinkerton, Frederick E. ;
Hwang, Son-Jong ;
Kim, Chul ;
Bowman, Robert C., Jr. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2008, 112 (47) :18661-18671
[2]   Modified lithium borohydrides for reversible hydrogen storage (2) [J].
Au, Ming ;
Jurgensen, Arthur ;
Zeigler, Kristine .
JOURNAL OF PHYSICAL CHEMISTRY B, 2006, 110 (51) :26482-26487
[3]   Nanosize-Controlled Reversibility for a Destabilizing Reaction in the LiBH4-NdH2+x System [J].
Cai, Weitong ;
Wang, Hui ;
Sun, Dalin ;
Zhu, Min .
JOURNAL OF PHYSICAL CHEMISTRY C, 2013, 117 (19) :9566-9572
[4]   AZn2(BH4)5 (A = Li, Na) and NaZn(BH4)3: Structural Studies [J].
Cerny, Radovan ;
Kim, Ki Chul ;
Penin, Nicolas ;
D'Anna, Vincenza ;
Hagemann, Hans ;
Sholl, David S. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2010, 114 (44) :19127-19133
[5]   Interaction between lithium amide and lithium hydride [J].
Chen, P ;
Xiong, ZT ;
Luo, JZ ;
Lin, JY ;
Tan, KL .
JOURNAL OF PHYSICAL CHEMISTRY B, 2003, 107 (39) :10967-10970
[6]   Interaction of hydrogen with metal nitrides and imides [J].
Chen, P ;
Xiong, ZT ;
Luo, JZ ;
Lin, JY ;
Tan, KL .
NATURE, 2002, 420 (6913) :302-304
[7]   In situ infrared (FTIR) study of the mechanism of the borohydride oxidation reaction [J].
Concha, B. Molina ;
Chatenet, M. ;
Maillard, F. ;
Ticianelli, E. A. ;
Lima, F. H. B. ;
de Lima, R. B. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (37) :11507-11516
[8]  
Custelcean R, 1999, ANGEW CHEM INT EDIT, V38, P1661, DOI 10.1002/(SICI)1521-3773(19990601)38:11<1661::AID-ANIE1661>3.0.CO
[9]  
2-O
[10]   The catalytic effect of additive Nb2O5 on the reversible hydrogen storage performances of LiBH4-MgH2 composite [J].
Fan, Mei-Qiang ;
Sun, Li-Xian ;
Zhang, Yao ;
Xu, Fen ;
Zhang, Jian ;
Chu, Hai-liang .
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 2008, 33 (01) :74-80