Nowadays, finding cheap and non-toxic materials able to reversibly store high amounts of hydrogen is a challenge in the renewable energy field. Metal sulfides seem to be promising candidates to this purpose. Titanium ...Nowadays, finding cheap and non-toxic materials able to reversibly store high amounts of hydrogen is a challenge in the renewable energy field. Metal sulfides seem to be promising candidates to this purpose. Titanium sulfides are reported to be particularly interesting but their ability to store hydrogen remains unclear. In this work, titanium based sulfides TiS2 and TiS3 with two-dimensional nanostructures have been synthesized by solid-gas reaction between titanium powder and sulfur at temperatures between 500-600℃. The morphology and crystal structure of Ti-sulfides were characterized by SEM （scanning electronic microscopy） equipped with EDX （energy dispersion X-ray） and XRD （X-ray diffraction）, respectively. Their thermal stability was examined by TGA （thermal gravimetric analysis）. Their hydrogenation properties have been determined by manometric means using a Sieverts system and by DSC-HP （high-pressure differential scanning calorimetric）. Ti-sulfides hardly absorb/adsorb hydrogen for hydrogen pressures up to 80 bar and reaction temperatures up to 300℃.展开更多
The Li-Mg-N-H hydrogen storage system is a promising hydrogen storage material due to its moderate operation temperature,good reversibility,and relatively high capacity.In this work,the Li-Mg-N-H composite was directl...The Li-Mg-N-H hydrogen storage system is a promising hydrogen storage material due to its moderate operation temperature,good reversibility,and relatively high capacity.In this work,the Li-Mg-N-H composite was directly synthesized by reactive ball milling(RBM) of Li3N and Mg powder mixture with a molar ratio of 2:1 under hydrogen pressure of 9 MPa.More than 8.8 wt%hydrogen was absorbed during the RBM process.The phases and structural evolution during the in situ hydrogenation process were analyzed by means of in situ solidgas absorption and ex situ X-ray diffraction(XRD) measurements.It is determined that the hydrogenation can be divided into two steps,leading to mainly the formation of a lithium magnesium imide phase and a poorly crystallized amide phase,respectively.The H-cycling properties of the as-milled composite were determined by temperature-programmed dehydrogenation(TPD) method in a closed system.The onset dehydrogenation temperature was detected at 125℃,and it can reversibly desorb 3.1 wt% hydrogen under a hydrogen back pressure of 0.2 MPa.The structural evolution during dehydrogenation was further investigated by in situ XRD measurement.It is found that Mg(NH_(2))_(2)phase disappears at about 200 ℃,and Li_(2)Mg_(2)N_(3)H_(3),LiNH_(2),and Li_(2)MgN_(2)H_(2)phases coexist at even 300 ℃,revealing that the dehydrogenation process is step-wised and only partial hydrogen can be desorbed.展开更多
Li-Mg-N-B-H/ZrCoH_(3) composites were successfully synthesized by ball milling of the reactants under argon and hydrogen atmosphere,respectively.The composite synthesized by reactive ball milling(RBM)under hydrogen ha...Li-Mg-N-B-H/ZrCoH_(3) composites were successfully synthesized by ball milling of the reactants under argon and hydrogen atmosphere,respectively.The composite synthesized by reactive ball milling(RBM)under hydrogen has the best hydrogen storage properties.It can desorb 3.71 wt%hydrogen in 60 min at 150℃under pressure of 0.1 MPa,and the dehydrogenation capacity reaches 4.59 wt%in 8 h.For the re-hydrogenation,5.27 wt%hydrogen was absorbed in only 10 min at 150℃under H_(2) pressure of 8 MPa.The phases of the as-milled and subsequently dehydrogenated and re-hydrogenated samples were determined by X-ray diffraction(XRD).The microstructures and elemental distributions were characterized by scanning electron microscope(SEM)and energy-dispersive spectrometer(EDS)measurements.It is shown that Mg is in situ hydrogenated and introduced homogeneous distribution of ZrCoH_(3) particles during the RBM process under hydrogen atmosphere.The activation energies for the composites were calculated by Kissinger method through differential scanning calorimetric(DSC)measurements for the dehydrogenation process with different heating rates.It is determined that the activation energy for the Li-Mg-N-B-H/ZrCoH_(3) composite synthesized by RBM under hydrogen is 79.9 kJ·mol^(-1),which is14 kJ·mol^(-1) lower than that for the sample without ZrCoH_(3) addition.The N-H bond energies were analyzed by infrared(IR)absorption spectrum,and the reasons for weakening of the N-H bond were further discussed.展开更多
文摘Nowadays, finding cheap and non-toxic materials able to reversibly store high amounts of hydrogen is a challenge in the renewable energy field. Metal sulfides seem to be promising candidates to this purpose. Titanium sulfides are reported to be particularly interesting but their ability to store hydrogen remains unclear. In this work, titanium based sulfides TiS2 and TiS3 with two-dimensional nanostructures have been synthesized by solid-gas reaction between titanium powder and sulfur at temperatures between 500-600℃. The morphology and crystal structure of Ti-sulfides were characterized by SEM （scanning electronic microscopy） equipped with EDX （energy dispersion X-ray） and XRD （X-ray diffraction）, respectively. Their thermal stability was examined by TGA （thermal gravimetric analysis）. Their hydrogenation properties have been determined by manometric means using a Sieverts system and by DSC-HP （high-pressure differential scanning calorimetric）. Ti-sulfides hardly absorb/adsorb hydrogen for hydrogen pressures up to 80 bar and reaction temperatures up to 300℃.
基金financially supported by the Beijing Science and Technology Program(No.D141100002014002)the European COST Action(No.MP1103)
文摘The Li-Mg-N-H hydrogen storage system is a promising hydrogen storage material due to its moderate operation temperature,good reversibility,and relatively high capacity.In this work,the Li-Mg-N-H composite was directly synthesized by reactive ball milling(RBM) of Li3N and Mg powder mixture with a molar ratio of 2:1 under hydrogen pressure of 9 MPa.More than 8.8 wt%hydrogen was absorbed during the RBM process.The phases and structural evolution during the in situ hydrogenation process were analyzed by means of in situ solidgas absorption and ex situ X-ray diffraction(XRD) measurements.It is determined that the hydrogenation can be divided into two steps,leading to mainly the formation of a lithium magnesium imide phase and a poorly crystallized amide phase,respectively.The H-cycling properties of the as-milled composite were determined by temperature-programmed dehydrogenation(TPD) method in a closed system.The onset dehydrogenation temperature was detected at 125℃,and it can reversibly desorb 3.1 wt% hydrogen under a hydrogen back pressure of 0.2 MPa.The structural evolution during dehydrogenation was further investigated by in situ XRD measurement.It is found that Mg(NH_(2))_(2)phase disappears at about 200 ℃,and Li_(2)Mg_(2)N_(3)H_(3),LiNH_(2),and Li_(2)MgN_(2)H_(2)phases coexist at even 300 ℃,revealing that the dehydrogenation process is step-wised and only partial hydrogen can be desorbed.
基金financially supported by Beijing Science and Technology Program(No.D141100002014002)。
文摘Li-Mg-N-B-H/ZrCoH_(3) composites were successfully synthesized by ball milling of the reactants under argon and hydrogen atmosphere,respectively.The composite synthesized by reactive ball milling(RBM)under hydrogen has the best hydrogen storage properties.It can desorb 3.71 wt%hydrogen in 60 min at 150℃under pressure of 0.1 MPa,and the dehydrogenation capacity reaches 4.59 wt%in 8 h.For the re-hydrogenation,5.27 wt%hydrogen was absorbed in only 10 min at 150℃under H_(2) pressure of 8 MPa.The phases of the as-milled and subsequently dehydrogenated and re-hydrogenated samples were determined by X-ray diffraction(XRD).The microstructures and elemental distributions were characterized by scanning electron microscope(SEM)and energy-dispersive spectrometer(EDS)measurements.It is shown that Mg is in situ hydrogenated and introduced homogeneous distribution of ZrCoH_(3) particles during the RBM process under hydrogen atmosphere.The activation energies for the composites were calculated by Kissinger method through differential scanning calorimetric(DSC)measurements for the dehydrogenation process with different heating rates.It is determined that the activation energy for the Li-Mg-N-B-H/ZrCoH_(3) composite synthesized by RBM under hydrogen is 79.9 kJ·mol^(-1),which is14 kJ·mol^(-1) lower than that for the sample without ZrCoH_(3) addition.The N-H bond energies were analyzed by infrared(IR)absorption spectrum,and the reasons for weakening of the N-H bond were further discussed.
