Investigation of the thermochemical transformations in the LiAlH4-LiNH2 system

被引:16
作者
Dolotko, Oleksandr
Kobayashi, Takeshi
Wiench, Jerzy W.
Pruski, Marek [2 ]
Pecharsky, Vitalij [1 ]
机构
[1] Iowa State Univ, Dept Mat Sci & Engn, Ames Lab, Ames, IA 50011 USA
[2] Iowa State Univ, Dept Chem, Ames, IA 50011 USA
关键词
Metal hydrides; Hydrogen storage; Thermal decomposition; Rehydrogenation; Solid-state NMR; X-ray diffraction; SOLID-STATE NMR; HYDROGEN STORAGE; COMPLEX HYDRIDES; THERMAL-DECOMPOSITION; QUADRUPOLAR NUCLEI; LITHIUM; DESTABILIZATION; SPECTROSCOPY; SENSITIVITY; IMIDES;
D O I
10.1016/j.ijhydene.2011.05.163
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The thermal transformations in the lithium alanate-amide system consisting of lithium aluminum hydride (LiAlH4) and lithium amide (LiNH2), mixed in a 1:1 M ratio, were investigated using the pressure-composition-temperature analysis, solid-state nuclear magnetic resonance, X-ray powder diffraction, and residual gas analysis. Below 250 degrees C, the alanate decomposes into Al, LiH and H-2, through the formation of Li3AlH6, whereas the amide remains largely intact. The release of gaseous hydrogen corresponds to approximately 5 wt%. Above 250 degrees C, additional 4 wt% of hydrogen is produced through solidstate reactions among LiNH2, LiH and metallic Al, through the formation of intermetallic Li-Al binary alloy and an unidentified intermediate. The overall reaction of the thermochemical transformation of the LiAlH4 LiNH2 mixture results in the production of Li3AlN2, metallic Al, LiH and the release of 9 wt% of gaseous hydrogen. The reaction mechanism of the thermal decomposition is different from one identified earlier during mechanical treatment of the same system. Rehydrogenation of the thermally-decomposed products of LiAlH4-LiNH2 mixture using high hydrogen pressure (180 bar) and heating (275 degrees C) yields LiNH2 and amorphous aluminum nitride (AlN). Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
引用
收藏
页码:10626 / 10634
页数:9
相关论文
共 38 条
[1]   Increasing the sensitivity of 2D high-resolution NMR methods applied to quadrupolar nuclei [J].
Amoureux, JP ;
Delevoye, L ;
Steuernagel, S ;
Gan, Z ;
Ganapathy, S ;
Montagne, L .
JOURNAL OF MAGNETIC RESONANCE, 2005, 172 (02) :268-278
[2]   Titanium catalyzed solid-state transformations in LiAlH4 during high-energy ball-milling [J].
Balema, VP ;
Wiench, JW ;
Dennis, KW ;
Pruski, M ;
Pecharsky, VK .
JOURNAL OF ALLOYS AND COMPOUNDS, 2001, 329 (1-2) :108-114
[3]   HETERONUCLEAR DECOUPLING IN ROTATING SOLIDS [J].
BENNETT, AE ;
RIENSTRA, CM ;
AUGER, M ;
LAKSHMI, KV ;
GRIFFIN, RG .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (16) :6951-6958
[4]   The decomposition of LiAlD4 studied by in-situ X-ray and neutron diffraction [J].
Brinks, HW ;
Hauback, BC ;
Norby, P ;
Fjellvåg, H .
JOURNAL OF ALLOYS AND COMPOUNDS, 2003, 351 (1-2) :222-227
[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]   Mechanochemical transformations in Li(Na)AlH4-Li(Na)NH2 systems [J].
Dolotko, Oleksandr ;
Zhang, Haiqiao ;
Ugurlu, Ozan ;
Wiench, Jerzy W. ;
Pruski, Marek ;
Chumbley, L. Scott ;
Pecharsky, Vitalij .
ACTA MATERIALIA, 2007, 55 (09) :3121-3130
[8]   ISOTROPIC SPECTRA OF HALF-INTEGER QUADRUPOLAR SPINS FROM BIDIMENSIONAL MAGIC-ANGLE-SPINNING NMR [J].
FRYDMAN, L ;
HARWOOD, JS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (19) :5367-5368
[9]   Enhancing MQMAS sensitivity using signals from multiple coherence transfer pathways [J].
Gan, ZH ;
Kwak, HT .
JOURNAL OF MAGNETIC RESONANCE, 2004, 168 (02) :346-351
[10]   THE THERMAL DECOMPOSITION OF LITHIUM ALUMINIUM HYDRIDE [J].
GARNER, WE ;
HAYCOCK, EW .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1952, 211 (1106) :335-351