The effects of Sr TiO_3 on the hydrogen storage properties of MgH_2 have been studied for the first time.The onset dehydrogenation temperature of the MgH_2-10 wt% SrTiO_3 is found to be 275 ℃, which is 55 ℃ lower as...The effects of Sr TiO_3 on the hydrogen storage properties of MgH_2 have been studied for the first time.The onset dehydrogenation temperature of the MgH_2-10 wt% SrTiO_3 is found to be 275 ℃, which is 55 ℃ lower as compared to the as-milled MgH_2. The composite is able to absorb 4.3 wt% of hydrogen in 60 min instead of 1.1 wt% for the as-milled Mg H_2. Meanwhile, the composite is able to release 5.3 wt% of hydrogen in 17 min compared to 1.9 wt% by the as-milled Mg H_2 at 320 ℃. The calculated Eaof the Mg H_2-10 wt% SrTiO_3 is 109 k J/mol, which is 26.3 kJ/mol lower than the calculated Eaof the as-milled MgH_2. The Sr TiO_3 is not decomposed during the ball milling and the re/dehydrogenation processes. The catalytic effect shown by the SrTiO_3 is owing to its ability to change the physical structure of the MgH_2 particles during the ball milling process.展开更多
In this study, the hydrogen storage properties of MgH-X wt% KNiF（X = 5, 10, 15, 20, and 50） were investigated for the first time. From the analysis of the onset desorption temperature and isothermal de/absorption ki...In this study, the hydrogen storage properties of MgH-X wt% KNiF（X = 5, 10, 15, 20, and 50） were investigated for the first time. From the analysis of the onset desorption temperature and isothermal de/absorption kinetics, it was shown that MgH+ 5 wt% KNiFsample has the best performance. The 5wt% doped sample started to release hydrogen at about 260 °C, which was a reduction of about 95 °C and 157 oC compared with the as-milled and as-received MgH. In addition, the de/absorption kinetics of the MgH+ 5 wt% KNiFwere also improved significantly compared to the un-doped MgH. The apparent activation energy for hydrogen desorption exhibited the decrement from 167.0 k J/mol for as-milled MgHto 111.0 k J/mol with the addition of 5 wt% KNiF. Moreover, the X-ray diffraction spectra displayed the formation of new phases of KF, KH, MgNi and MgNiHby doping the KNiFwith MgHafter the dehydrogenation and rehydrogenation processes. The scanning electron microscope results revealed that MgHdoped with 5 wt% KNiFdemonstrated the smallest particle size compared to the as-received and as-milled MgH. It is believed that the formation of in situ active species of KF, KH, and MgNi could provide a synergetic catalytic effect in enhancing the hydrogen sorption properties of MgH.展开更多
In order to improve the hydrogen storage properties of LiBH4-MgH2 composite, two different kinds of Nb-based catalysts, NbC and NbF5, were added to LiBH4-MgH2 composite by ball milling, and the effect of catalysts on ...In order to improve the hydrogen storage properties of LiBH4-MgH2 composite, two different kinds of Nb-based catalysts, NbC and NbF5, were added to LiBH4-MgH2 composite by ball milling, and the effect of catalysts on hydrogen storage properties of the modified LiBH4-MgH2 system was investigated. The experimental results show that LiBH4-MgH2 composite is a two-step dehydrogenation process, and Nb-based compounds can remarkably enhance its dehydrogenation kinetics. For the composite without addition of catalysts, the starting decomposition temperature for the first dehydrogenation step is around 320℃, and there is a long period of incubation time（around 220 min） for the occurrence of the second decomposition step even at high temperature of 450℃. It needs more than 10 h to complete the decomposition process and release around 9 wt% H2. After addition of 5 mol% NbF5, the starting decomposition temperature for the first dehydrogenation step is around 150℃, there is no incubation time for the second decomposition step, and it takes around 40 min to complete the second step and reaches a total dehydrogenation capacity of 9.5 wt%. NbF5 has better catalytic effect than NbC. Based on the hydrogenation/dehydrogenation behaviors and structural variation, the mechanism of catalytic effect was discussed.展开更多
Based on experimental results that VH0.81/MgH2 interface was found during the process of mechanically milling MgH2+5at.%V nanocomposite, H atoms diffusion and adsorption properties of MgH2-V systems have been investig...Based on experimental results that VH0.81/MgH2 interface was found during the process of mechanically milling MgH2+5at.%V nanocomposite, H atoms diffusion and adsorption properties of MgH2-V systems have been investigated by using a first-principles plane-wave pseudopotential method based on the density functional theory. The results are as follows. When VH/MgH2 interface is formed due to V alloying MgH2 phase, the vacancy formed by H atoms near VH phase region is more stable than that without V alloying, while vacancy near MgH2 phase region is less stable than that without V alloying. During the process of H atoms diffusion after V alloying, the max migration barrier energy of H atoms in MgH2-V systems is reduced compared with that of MgH2 phase, which means that H atoms diffuse easily. When H diffuses into VH from MgH2 across VH/MgH2 interface, among three substitutions such as the replacement of H for V vacancy, or interstitial site or V atoms, the replacement of H for V vacancy has the strongest diffusion ability, next interstitial site, and finally V atoms site. As far as H adsorbed on different surfaces of VH phase is concerned, physical adsorption is carried out more easily than chemical adsorption, and the behavior of H atoms adsorbed on the surface near VH phase region can be found more easily than that near MgH2 phase region.展开更多
基金financially supported by the Ministry of Higher Education Malaysia under the Fundamental Research Grant Scheme (FRGS 59362)
文摘The effects of Sr TiO_3 on the hydrogen storage properties of MgH_2 have been studied for the first time.The onset dehydrogenation temperature of the MgH_2-10 wt% SrTiO_3 is found to be 275 ℃, which is 55 ℃ lower as compared to the as-milled MgH_2. The composite is able to absorb 4.3 wt% of hydrogen in 60 min instead of 1.1 wt% for the as-milled Mg H_2. Meanwhile, the composite is able to release 5.3 wt% of hydrogen in 17 min compared to 1.9 wt% by the as-milled Mg H_2 at 320 ℃. The calculated Eaof the Mg H_2-10 wt% SrTiO_3 is 109 k J/mol, which is 26.3 kJ/mol lower than the calculated Eaof the as-milled MgH_2. The Sr TiO_3 is not decomposed during the ball milling and the re/dehydrogenation processes. The catalytic effect shown by the SrTiO_3 is owing to its ability to change the physical structure of the MgH_2 particles during the ball milling process.
基金supported by Ministry of Higher Education Malaysia Fundamental Research Grant Scheme(FRGS 59362)
文摘In this study, the hydrogen storage properties of MgH-X wt% KNiF（X = 5, 10, 15, 20, and 50） were investigated for the first time. From the analysis of the onset desorption temperature and isothermal de/absorption kinetics, it was shown that MgH+ 5 wt% KNiFsample has the best performance. The 5wt% doped sample started to release hydrogen at about 260 °C, which was a reduction of about 95 °C and 157 oC compared with the as-milled and as-received MgH. In addition, the de/absorption kinetics of the MgH+ 5 wt% KNiFwere also improved significantly compared to the un-doped MgH. The apparent activation energy for hydrogen desorption exhibited the decrement from 167.0 k J/mol for as-milled MgHto 111.0 k J/mol with the addition of 5 wt% KNiF. Moreover, the X-ray diffraction spectra displayed the formation of new phases of KF, KH, MgNi and MgNiHby doping the KNiFwith MgHafter the dehydrogenation and rehydrogenation processes. The scanning electron microscope results revealed that MgHdoped with 5 wt% KNiFdemonstrated the smallest particle size compared to the as-received and as-milled MgH. It is believed that the formation of in situ active species of KF, KH, and MgNi could provide a synergetic catalytic effect in enhancing the hydrogen sorption properties of MgH.
基金financially supported by the National Natural Science Foundation of China(Nos.51471149 and 51171168)the Public Project of Zhejiang Province(No.2015C31029)
文摘In order to improve the hydrogen storage properties of LiBH4-MgH2 composite, two different kinds of Nb-based catalysts, NbC and NbF5, were added to LiBH4-MgH2 composite by ball milling, and the effect of catalysts on hydrogen storage properties of the modified LiBH4-MgH2 system was investigated. The experimental results show that LiBH4-MgH2 composite is a two-step dehydrogenation process, and Nb-based compounds can remarkably enhance its dehydrogenation kinetics. For the composite without addition of catalysts, the starting decomposition temperature for the first dehydrogenation step is around 320℃, and there is a long period of incubation time（around 220 min） for the occurrence of the second decomposition step even at high temperature of 450℃. It needs more than 10 h to complete the decomposition process and release around 9 wt% H2. After addition of 5 mol% NbF5, the starting decomposition temperature for the first dehydrogenation step is around 150℃, there is no incubation time for the second decomposition step, and it takes around 40 min to complete the second step and reaches a total dehydrogenation capacity of 9.5 wt%. NbF5 has better catalytic effect than NbC. Based on the hydrogenation/dehydrogenation behaviors and structural variation, the mechanism of catalytic effect was discussed.
基金the Ministry of Science and Technology of China (Grant No. 2006CB605104)the National Natural Science Foundation of China (Grant No. 50771044)
文摘Based on experimental results that VH0.81/MgH2 interface was found during the process of mechanically milling MgH2+5at.%V nanocomposite, H atoms diffusion and adsorption properties of MgH2-V systems have been investigated by using a first-principles plane-wave pseudopotential method based on the density functional theory. The results are as follows. When VH/MgH2 interface is formed due to V alloying MgH2 phase, the vacancy formed by H atoms near VH phase region is more stable than that without V alloying, while vacancy near MgH2 phase region is less stable than that without V alloying. During the process of H atoms diffusion after V alloying, the max migration barrier energy of H atoms in MgH2-V systems is reduced compared with that of MgH2 phase, which means that H atoms diffuse easily. When H diffuses into VH from MgH2 across VH/MgH2 interface, among three substitutions such as the replacement of H for V vacancy, or interstitial site or V atoms, the replacement of H for V vacancy has the strongest diffusion ability, next interstitial site, and finally V atoms site. As far as H adsorbed on different surfaces of VH phase is concerned, physical adsorption is carried out more easily than chemical adsorption, and the behavior of H atoms adsorbed on the surface near VH phase region can be found more easily than that near MgH2 phase region.
