Improved reversible hydrogen storage of LiAlH 4 by nano-sized TiH 2 Shu-Sheng Liu a,b , Zhi-Bao Li b , Cheng-Li Jiao b , Xiao-Liang Si a , Li-Ni Yang d , Jian Zhang b , Huai-Ying Zhou a , Feng-Lei Huang e , Zelimir Gabelica f , Christoph Schick g , Li-Xian Sun a,b, *, Fen Xu a,c, * a Department of Material Science & Engineering, Guilin University of Electrical Technology, Guilin 541004, China b Materials and Thermochemistry Laboratory, Dalian National Laboratory of Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China c Faculty of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, China d College of Chemistry, Liaoning University, Shenyang 110036, China e State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081, China f Universite ´ de Haute Alsace, ENSCMu, Lab. LPI-GSEC, 3, Rue A. Werner, Mulhouse Cedex F-68094, France g Institute of Physics, Universita ¨t Rostock, Rostock D-18051, Germany article info Article history: Received 10 September 2012 Received in revised form 6 November 2012 Accepted 7 November 2012 Available online 10 January 2013 Keywords: Titanium hydride Alanate Catalyst Dehydrogenation Regeneration abstract Transition metal halides are mostly used as dopants to improve the hydrogen storage properties of LiAlH 4 , but they will cause hydrogen capacity loss because of their relatively high molecular weights and reactions with LiAlH 4 . To overcome these drawbacks, active nano-sized TiH 2 (TiH 2 nano ) prepared by reactive ball milling is used to dope LiAlH 4 . It shows superior catalytic effect on the dehydrogenation of LiAlH 4 compared to commercial TiH 2 . TiH 2 nano -doped LiAlH 4 starts to release hydrogen at 75  C, which is 80  C lower than the onset dehydrogenation temperature of commercial LiAlH 4 . About 6.3 wt.% H 2 can be released isothermally at 100  C (800 min) or at 120  C (150 min). The apparent activation energies of the first two dehydrogenation reactions of LiAlH 4 are reduced by about 20 and 24 kJ mol 1 , respectively. Meanwhile, the regeneration of LiAlH 4 is realized through extracting the solvent from LiAlH 4 $4THF, which is obtained by ball milling the dehydro- genated products of TiH 2 nano -doped LiAlH 4 in the presence of THF and 5 MPa H 2 . This suggests that TiH 2 is also an effective catalyst for the formation of LiAlH 4 $4THF. Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. 1. Introduction The storage of hydrogen is the main roadblock in the use of hydrogen. Among the methods of hydrogen storage, solid- state storage in metal hydrides, complex hydrides or chem- ical hydrides has been intensively investigated these years [1,2]. Alanates (like NaAlH 4 and LiAlH 4 ) are accepted as a class of promising candidates for on-board application. In 1997, NaAlH 4 was discovered to be reversible under moderate conditions [3]. Since then, a lot of works have been done on NaAlH 4 . But it can not fulfill the U.S. Department of Energy’s ultimate goal (7.5 wt.% H 2 ) for a hydrogen storage system [4]. * Corresponding authors. Department of Material Science & Engineering, Guilin University of Electrical Technology, Guilin 541004, China. Tel./fax: þ86 411 84379213. E-mail addresses: lxsun@dicp.ac.cn (L.-X. Sun), xufen@lnnu.edu.cn (F. Xu). Available online at www.sciencedirect.com journal homepage: www.elsevier.com/locate/he international journal of hydrogen energy 38 (2013) 2770 e2777 0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.ijhydene.2012.11.042