Markmaitree Tippawan, Ren Ruiming, Shaw Leon L
Department of Materials Science and Engineering, University of Connecticut, Storrs, Connecticut, USA.
J Phys Chem B. 2006 Oct 19;110(41):20710-8. doi: 10.1021/jp060181c.
The decomposition of lithium amide (LiNH2) to lithium imide (Li2NH) and ammonia (NH3) with and without high-energy ball milling is investigated to lay a foundation for identifying methods to enhance the hydrogen uptake/release of the lithium amide and lithium hydride mixture. A wide range of analytical instruments are utilized to provide unambiguous evidence of the effect of mechanical activation. It is shown that ball milling reduces the onset temperature for the decomposition of LiNH2 from 120 degrees C to room temperature. The enhanced decomposition via ball milling is attributed to mechanical activation related to the formation of nanocrystallites, the reduced particle size, the increased surface area, and the decreased activation energy. The more mechanical activation there is, then the more improvement there is in enhancing the decomposition of LiNH2. It also is found that the activation energy for the decomposition of LiNH2 without ball milling is 243.98 kJ/mol, which is reduced to 222.20 kJ/mol after ball milling at room temperature for 45 min and is further reduced to 138.05 kJ/mol after ball milling for 180 min. The rate of the isothermal decomposition at the later phase of the LiNH2 decomposition is controlled by diffusion of NH3 through the Li2NH layer.
研究了在有和没有高能球磨的情况下,氨基锂(LiNH₂)分解为亚氨基锂(Li₂NH)和氨(NH₃)的过程,为确定增强氨基锂和氢化锂混合物吸氢/放氢的方法奠定基础。使用了多种分析仪器来提供机械活化效果的确切证据。结果表明,球磨将LiNH₂分解的起始温度从120℃降低到室温。通过球磨增强的分解归因于与纳米微晶形成、粒径减小、表面积增加和活化能降低相关的机械活化。机械活化越多,增强LiNH₂分解的效果就越好。还发现,未进行球磨时LiNH₂分解的活化能为243.98 kJ/mol,在室温下球磨45分钟后降至222.20 kJ/mol,球磨180分钟后进一步降至138.05 kJ/mol。LiNH₂分解后期的等温分解速率由NH₃通过Li₂NH层的扩散控制。