Lin Huai-Jun, Li Hai-Wen, Paik Biswajit, Wang Jianhui, Akiba Etsuo
International Research Centre for Hydrogen Energy, Kyushu University, Fukuoka, Japan.
Dalton Trans. 2016 Oct 21;45(39):15374-15381. doi: 10.1039/c6dt02845d. Epub 2016 Sep 6.
The three-component Mg(NH)-LiNH-4LiH composite reversibly stores hydrogen exceeding 5 wt% at a temperature as low as 150 °C. In this work, a number of additives such as CeF, CeO, TiCl, TiH, NaH, KBH and KH are added to the Mg(NH)-LiNH-4LiH composite in order to improve its kinetics, thermodynamics and cycling properties. Addition of 3 wt% of KH reduces the dehydrogenation onset temperature of the Mg(NH)-LiNH-4LiH composite to below 90 °C without emission of NH during the whole dehydrogenation process up to 450 °C. Moreover, the dehydrogenation kinetics and cycling ability are remarkably enhanced upon KH-addition. The reaction model of the Mg(NH)-LiNH-4LiH composite is altered upon KH-addition with the active molecule density improved by about 200 times. In addition, by optimization of the ratio of Mg to Li in the Mg(NH)-LiNH-LiH system, several novel composites, e.g., Mg(NH)-2LiNH-5.9LiH-0.1KH and Mg(NH)-LiNH-5.9LiH-0.1KH, with the hydrogen storage capacity exceeding 6 wt% without emission of NH below 250 °C are developed. Our study demonstrates that there are various undiscovered candidates with promising hydrogen storage properties in the three-component Li-Mg-N-H system.
由镁氨化物-锂氨化物-4氢化锂组成的三组分复合材料,在低至150℃的温度下可实现可逆储氢,储氢量超过5 wt%。在本研究中,向镁氨化物-锂氨化物-4氢化锂复合材料中添加了多种添加剂,如氟化铈、氧化铈、四氯化钛、氢化钛、氢化钠、硼氢化钾和氢化钾,以改善其动力学、热力学和循环性能。添加3 wt%的氢化钾可将镁氨化物-锂氨化物-4氢化锂复合材料的脱氢起始温度降低至90℃以下,在高达450℃的整个脱氢过程中无氨气释放。此外,添加氢化钾后脱氢动力学和循环能力显著增强。添加氢化钾后,镁氨化物-锂氨化物-4氢化锂复合材料的反应模型发生改变,活性分子密度提高了约200倍。此外,通过优化镁氨化物-锂氨化物-氢化锂体系中镁与锂的比例,开发出了几种新型复合材料,如镁氨化物-2锂氨化物-5.9氢化锂-0.1氢化钾和镁氨化物-锂氨化物-5.9氢化锂-0.1氢化钾,在250℃以下储氢量超过6 wt%且无氨气释放。我们的研究表明,在锂-镁-氮-氢三元体系中存在各种具有潜在储氢性能的未被发现的候选材料。