As a hydrogen storage material,both AlH_(3)and LiNH_(2)possess a high hydrogen capacity.However,the dehydrogenated AlH_(3)can hardly absorb hydrogen under normal conditions,while LiNH_(2)will generate NH_(3)rather tha...As a hydrogen storage material,both AlH_(3)and LiNH_(2)possess a high hydrogen capacity.However,the dehydrogenated AlH_(3)can hardly absorb hydrogen under normal conditions,while LiNH_(2)will generate NH_(3)rather than H_(2)upon decomposition.In this work,we report thatthe combination of AlH_(3)and LiNH_(2)through simple ball milling leads to partial reversibility of the AlH_(3)-LiNH_(2)system and the suppression of NH_(3)liberation.The negatively charged H^(δ-)in AlH_(3)will react with the positively charged H^(δ+)in LiNH_(2)through a redox reaction to form Li_(2)NH,AlN,and H_(2)at 120-170℃.After dehydrogenation at above 270℃,Li_(3)AlN_(2)is generated,which is crucial for the reversibility of this system.The more the Li3AlN2generated,the better the reversibility of this system.The dehydrogenation capacity of AlH_(3)+2LiNH_(2)at the third cycle(3.0 wt%)is higher than that of AlH_(3)+LiNH_(2)(1.2 wt%)due to the generation of more Li3AlN2.The role of AIH_(3)/Al in the AlH_(3)-LiNH_(2)system is to fix the nitrogen into the form of AIN and Li_(3)AlN_(2)and thus suppress the liberation of NH_(3).Therefore,the synergy of AlH_(3)and LiNH_(2)leads to the reversibility of the Li-Al-NH system and the suppression of NH_(3).展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22379030,52001079,52261038)the Science and Technology Department of Guangxi Zhuang Autonomous(Nos.2024JJG160001,GuiKeAD21238022)the Innovation Project of Guangxi Graduate Education(No.YCBZ2023011)
文摘As a hydrogen storage material,both AlH_(3)and LiNH_(2)possess a high hydrogen capacity.However,the dehydrogenated AlH_(3)can hardly absorb hydrogen under normal conditions,while LiNH_(2)will generate NH_(3)rather than H_(2)upon decomposition.In this work,we report thatthe combination of AlH_(3)and LiNH_(2)through simple ball milling leads to partial reversibility of the AlH_(3)-LiNH_(2)system and the suppression of NH_(3)liberation.The negatively charged H^(δ-)in AlH_(3)will react with the positively charged H^(δ+)in LiNH_(2)through a redox reaction to form Li_(2)NH,AlN,and H_(2)at 120-170℃.After dehydrogenation at above 270℃,Li_(3)AlN_(2)is generated,which is crucial for the reversibility of this system.The more the Li3AlN2generated,the better the reversibility of this system.The dehydrogenation capacity of AlH_(3)+2LiNH_(2)at the third cycle(3.0 wt%)is higher than that of AlH_(3)+LiNH_(2)(1.2 wt%)due to the generation of more Li3AlN2.The role of AIH_(3)/Al in the AlH_(3)-LiNH_(2)system is to fix the nitrogen into the form of AIN and Li_(3)AlN_(2)and thus suppress the liberation of NH_(3).Therefore,the synergy of AlH_(3)and LiNH_(2)leads to the reversibility of the Li-Al-NH system and the suppression of NH_(3).
