Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation inc...Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e., -23 kJ/molnz for LiOH-LiH, 55.34 kJ/moln: for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150 ℃; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molHz, and the corresponding entropy was ca. 101.23 J/(molHz .K), so the temperature for releasing 1.0 bar H2 was as high as 518 ℃, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.展开更多
基金supported by the National Natural Science Foundation of China(51301161)973 Project(2010CB631304)the Project of National Natural Science Funds for Distinguished Young Scholar(51225206)
文摘Alkali metal hydroxide and hydride composite systems contain both protic (H bonded with O) and hydridic hydrogen. The interaction of these two types of hydrides produces hydrogen. The enthalpy of dehydrogenation increased with the increase of atomic number of alkali metals, i.e., -23 kJ/molnz for LiOH-LiH, 55.34 kJ/moln: for NaOH-NaH and 222 kJ/molH2 for KOH-KH. These thermodynamic calculation results were consistent with our experimental results. H2 was released from LiOH-LiH system during ball milling. The dehydrogenation temperature of NaOH-NaH system was about 150 ℃; whereas KOH and KH did not interact with each other during the heating process. Instead, KH decomposed by itself. In these three systems, NaOH-NaH was the only reversible hydrogen storage system, the enthalpy of dehydrogenation was about 55.65 kJ/molHz, and the corresponding entropy was ca. 101.23 J/(molHz .K), so the temperature for releasing 1.0 bar H2 was as high as 518 ℃, showing unfavorable thermodynamic properties. The activation energy for hydrogen desorption of NaOH-NaH was found to be 57.87 kJ/mol, showing good kinetic properties.