Ammonia Desorption Property and Structural Changes of LiAl(NH2)(4) on Thermal Decomposition

作者:Ono Taisuke; Shimoda Keiji; Tsubota Masami; Kohara Shinji; Ichikawa Takayuki*; Kojima Ken ichi; Tansho Masataka; Shimizu Tadashi; Kojima Yoshitsugu
来源:Journal of Physical Chemistry C, 2011, 115(20): 10284-10291.
DOI:10.1021/jp111656v

摘要

A composite material of LiAl(NH2)(4) and LiH irreversibly releases H-2 gas by 6.1 mass% below 130 degrees C. The H-2 desorption mechanism of the composite has been proposed, but it is still controversial because the decomposition mechanism of LiAl(NH2)(4) is not well-known. We here examined the gas desorption property of LiAl(NH2)(4) by using thermogravimetry and mass spectroscopy. On heating to 160 degrees C, a large amount of NH3 release was observed, which was followed by mild gas emission until 500 degrees C. We investigated the detailed structural changes on the NH3 gas desorption by using synchrotron X-ray total scattering, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. On the basis of these structural analyses, we obtained, strong evidence that the amorphous intermediate product described as LiAl(NH2)x(NH)(y)N-z was formed during the thermal decomposition process, where the AlN4 network polymerization proceeds and the ratio of [NH2](-), [NH](2-), and [N](3-) units gradually changes with releasing NH3 gas. Finally, the crystalline Li3AlN2 and the amorphous residue, which will become AlN with longer annealing, were formed because of the complete exhaustion of hydrogen atoms by NH3 desorption.

  • 出版日期2011-5-26