Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, PR China.
Dalton Trans. 2013 Apr 21;42(15):5524-31. doi: 10.1039/c3dt32165g. Epub 2013 Feb 22.
The Mg(NH2)2-2LiH composite is a promising hydrogen storage material due to its relatively high reversible hydrogen capacity (~5.6 wt%) and suitable thermodynamic properties that allow hydrogen sorption conducting at temperatures below 90 °C. However, the presence of a severe kinetic barrier inhibits its low-temperature operation. In the present work, Li3AlH6 was introduced to the Mg(NH2)2-2LiH system. Experimental results show that a 3.2% mol Li3AlH6-modified Mg(NH2)2-2LiH sample released hydrogen at a rate ca. 4.5 times as fast as that of the Li3AlH6-free sample at 140 °C. The enhancement of desorption kinetics was simultaneously demonstrated by activation energy (Ea) of ca. 96.3 ± 9 kJ mol(-1) which was significantly decreased by 31 kJ mol(-1) from that of the Li3AlH6-free sample. The interaction of Li3AlH6 and Mg(NH2)2 during ball milling results in the formation of LiAl(NH)2, LiNH2 and Mg3N2. LiAl(NH)2 was actually the active species for the enhancement of dehydrogenation/re-hydrogenation kinetics of the system.
Mg(NH2)2-2LiH 复合材料是一种很有前途的储氢材料,因为它具有较高的可逆氢容量(~5.6wt%)和合适的热力学性质,允许在低于 90°C 的温度下进行吸氢反应。然而,存在严重的动力学障碍抑制了其在低温下的运行。在本工作中,将 Li3AlH6 引入到 Mg(NH2)2-2LiH 体系中。实验结果表明,在 140°C 下,与不含 Li3AlH6 的样品相比,添加了 3.2%摩尔 Li3AlH6 的 Mg(NH2)2-2LiH 样品的释氢速率快约 4.5 倍。通过约 96.3 ± 9 kJ mol(-1)的活化能(Ea)证明了脱氢动力学的增强,与不含 Li3AlH6 的样品相比,Ea 降低了 31 kJ mol(-1)。球磨过程中 Li3AlH6 和 Mg(NH2)2 的相互作用导致 LiAl(NH)2、LiNH2 和 Mg3N2 的形成。LiAl(NH)2 实际上是增强体系脱氢/再氢化动力学的活性物质。