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1.
LiBH4 is regarded as a promising hydrogen storage material due to its high hydrogen density. In this study, the dehydrogenation properties of LiBH4 were remarkably enhanced by doping hydrogenated Mg3RE compounds (RE denotes La, Ce, Nd rare earth metals), which are composed of nanostructured MgH2 and REH2+x (denoted as H − Mg3RE). For the LiBH4 + H − Mg3La mixture, the component LiBH4 desorbed 6 wt.% hydrogen even at a relatively low temperature of 340 °C, far lower than the desorption temperature of pure LiBH4 or the 2LiBH4 + MgH2 system. This kinetic improvement is attributed to the hydrogen exchange mechanism between the H − Mg3La and LiBH4, in the sense that the decomposition of MgH2 and LaH2+x catalyzed the dehydrogenation of LiBH4 through hydrogen exchange effect rather than mutual chemical reaction requiring higher temperature and hydrogen pressure. However, prior to fast hydrogen release, the hydrogen exchange effect suppressed the dehydriding of MgH2 and elevated its desorption temperature. It is expected to strengthen the hydrogen exchange effect by compositing the LiBH4 with other nanosized metal hydrides and to obtain better dehydrogenation properties.  相似文献   

2.
Two composite hydrogen storage materials based on Mg2FeH6 were investigated for the first time. The Mg2FeH6–LiBH4 composite of molar ratio 1:5 showed a hydrogen desorption capacity of 5.6 wt.% at 370 °C, and could be rehydrogenated to 3.6 wt.% with the formation of MgH2, as the material was heated to 445 °C and held at this temperature. The Mg2FeH6–LiNH2 composite of 3:10 molar ratio exhibited a hydrogen desorption capacity of 4.3 wt.% and released hydrogen at 100 °C lower then the Mg2FeH6–LiBH4 composite, but this mixture could not be rehydrogenated. Compared to neat Mg2FeH6, both composites show enhanced hydrogen storage properties in terms of desorption kinetics and capacity at these low temperatures. In particular, Mg2FeH6–LiNH2 exhibits a much lower desorption temperature than neat Mg2FeH6, but only Mg2FeH6–LiBH4 re-absorbs hydrogen.  相似文献   

3.
It is well known that the dehydrogenation pathway of the LiBH4–MgH2 composite system is highly reliant on whether decomposition is performed under vacuum or a hydrogen back-pressure. In this work, the effects of hydrogen back-pressure and NbF5 addition on the dehydrogenation kinetics of the LiBH4–MgH2 system are studied under either vacuum or hydrogen back-pressure, as well as the subsequent rehydrogenation and cycling. For the pristine sample, faster desorption kinetics was obtained under vacuum, but the performance is compromised by slow absorption kinetics. In contrast, hydrogen back-pressure remarkably promotes the absorption kinetics and increases the reversible hydrogen storage capacity, but with the penalty of much slower desorption kinetics. These drawbacks were overcome after doping with NbF5, with which the dehydrogenation and rehydrogenation kinetics was significantly improved. In particular, the enhanced kinetics was observed to persist well, even after 9 cycles, in the case of the NbF5 doped sample under hydrogen back-pressure, as well as the suppression of forming Li2B12H12. Furthermore, the mechanism that is behind these effects of NbF5 additive on the reversible dehydrogenation reaction of the LiBH4–MgH2 system is discussed.  相似文献   

4.
LiBH4+1/2MgH2 is a promising reactive hydride composite for hydrogen storage. In the present study, three Ce-based additives were used as catalysts to enhance the hydrogen storage performance of LiBH4+1/2MgH2 composites. The composites with Ce additives demonstrated significantly improved dehydrogenation kinetics and cyclic stability compared with the pure composite. X-ray diffraction and scanning electron microscopy analyses clearly revealed the phase transitions and morphological evolution during the hydriding-dehydriding cycling. The composites with Ce-based additives displayed stable nanostructures, in contrast to the rapid microstructural deterioration in the uncatalyzed composite. The CeB6 formed in the composites had a particle size of 10 nm after five cycles. It may act as the nucleus for MgB2 formation during dehydrogenation and thus account for the structural and performance stability of the composites upon cycling.  相似文献   

5.
Rehydrogenation behavior of 6LiBH4 + CaH2 composite with NbF5 has been studied between 350 and 500 °C after dehydrogenation at 450 °C. The composite exhibits the best rehydrogenation feature at 450 °C in terms of the overall rehydrogenation rate and the amount of absorbed hydrogen. It is found that about 9 wt% hydrogen is absorbed at 450 °C for 12 h. Up to 10 dehydrogenation–hydrogenation cycles have been carried out for the composite. It is demonstrated that 6LiBH4 + CaH2 with 15 wt% NbF5 maintains a reversible hydrogen storage capacity of about 6 wt% at 450 °C after a slight degradation between the 1st and 5th cycles. The addition of NbF5 seems to improve the cycle properties by retarding microstructural coarsening during cycles.  相似文献   

6.
In order to increase the hydrogen storage capacity of Mg-based materials, a mixture with a composition of 2LiBH4 + MgF2 and LiBH4, which has a hydrogen storage capacity of 18.4 wt%, were added to MgH2. Ti isopropoxide was also added to MgH2 as a catalyst. A MgH2 composite with a composition of 40 wt%MgH2 + 25 wt%LiBH4 + 30 wt% (2LiBH4 + MgF2) + 5 wt%Ti isopropoxide (corresponding to 40 wt%MgH2 + 37 wt%LiBH4 + 18 wt%MgF2 + 5 wt%Ti isopropoxide) was prepared by reactive mechanical grinding. The hydrogen storage properties of the sample were then examined. Hydrogen content vs. desorption time curves for consecutive 1st desorptions of 40 wt%MgH2 + 37 wt%LiBH4 + 18 wt%MgF2 + 5 wt%Ti isopropoxide from room temperature to 823 K showed that the total desorbed hydrogen quantity for consecutive 1st desorptions was 8.30 wt%.  相似文献   

7.
LiBH4 nano-particles are incorporated into mesoporous TiO2 scaffolds via a chemical impregnation method. And the enhanced desorption properties of the composite have been investigated. The LiBH4/TiO2 sample starts to release hydrogen at 220 °C and the maximal desorption peak occurs at about 330 °C, much lower compared to the bulk LiBH4. Furthermore, the composite exhibits excellent dehydrogenation kinetics, with 11 wt% of hydrogen liberated from LiBH4 at 300 °C within 3 h. X-ray diffraction and Fourier transform infrared spectroscopy are used to confirm the nanostructure of LiBH4 in the TiO2 scaffold. This work demonstrates that confinement within active porous scaffold host is a promising approach for enhancing hydrogen decomposition properties of light-metal complex hydrides.  相似文献   

8.
In the present work, the role of NbF5 addition amount in affecting the comprehensive hydrogen storage properties (dehydrogenation, rehydrogenation, cycling performance, hydrogen capacity) of 2LiBH4–MgH2 system as well as the catalytic mechanism of NbF5 have been systematically studied. It is found that increasing the addition amount of NbF5 to the 2LiBH4–MgH2 system not only results in dehydrogenation temperature reduction and hydriding–dehydriding kinetics enhancement but also leads to the de/rehydrogenation capacity loss. Compared with other samples, 2LiBH4–MgH2 doping with NbF5 in weight ratios of 40:4 exhibits superior comprehensive hydrogen storage properties, which can stably release ∼8.31 wt.% hydrogen within 2.5 h under 4 bar H2 and absorb ∼8.79 wt.% hydrogen within 10 min under 65 bar H2 at 400 °C even up to 20 cycling. As far as we know, this is the first time that excellent reversibility as high as 20 cycles without obvious degradation tendency in both of hydrogen capacity and reaction rate has been achieved in the 2LiBH4–MgH2 system. The further experimental study reveals that the highly catalytic effects of NbF5 on the 2LiBH4–MgH2 system are derived from the reaction between NbF5 and LiBH4, which provides a fundamental insight into the catalytic mechanism of NbF5.  相似文献   

9.
2LiBH4/MgH2 system is a representative and promising reactive hydride composite for hydrogen storage. However, the high desorption temperature and sluggish desorption kinetics hamper its practical application. In our present report, we successfully introduce CoNiB nanoparticles as catalysts to improve the dehydrogenation performances of the 2LiBH4/MgH2 composite. The sample with CoNiB additives shows a significant desorption property. Temperature programmed desorption (TPD) measurement demonstrates that the peak decomposition temperatures of MgH2 and LiBH4 are lowered to be 315 °C and 417 °C for the CoNiB-doped 2LiBH4/MgH2. Isothermal dehydrogenation analysis demonstrates that approximately 10.2 wt% hydrogen can be released within 360 min at 400 °C. In addition, this study gives a preliminary evidence for understanding the CoNiB catalytic mechanism of 2LiBH4/MgH2  相似文献   

10.
In this study, we report the hydrogen absorption/desorption properties and reaction mechanism of the MgH2-NaAlH4 (4:1) composite system. This composite system showed improved dehydrogenation performance compared with that of as-milled NaAlH4 and MgH2 alone. The dehydrogenation process in the MgH2-NaAlH4 composite can be divided into four stages: NaAlH4 is first reacted with MgH2 to form a perovskite-type hydride, NaMgH3 and Al. In the second dehydrogenation stage, the Al phase reacts with MgH2 to form Mg17Al12 phase accompanied with the self-decomposition of the excessive MgH2. NaMgH3 goes on to decompose to NaH during the third dehydrogenation stage, and the last stage is the decomposition of NaH. Kissinger analysis indicated that the apparent activation energy, EA, for the MgH2-relevent decomposition in MgH2-NaAlH4 composite was 148 kJ/mol, which is 20 kJ/mol less than for as-milled MgH2 (168 kJ/mol). X-ray diffraction patterns indicate that the second, third, and fourth stages are fully reversible. It is believed that the formation of Al12Mg17 phase during the dehydrogenation process alters the reaction pathway of the MgH2-NaAlH4 (4:1) composite system and improves its thermodynamic properties.  相似文献   

11.
The composites of (NaBH4+2Mg(OH)2) and (LiBH4+2Mg(OH)2) without and with nanometric Ni (n-Ni) added as a potential catalyst were synthesized by high energy ball milling. The ball milled NaBH4-based composite desorbs hydrogen in one exothermic reaction in contrast to its LiBH4-based counterpart which dehydrogenates in two reactions: an exothermic and endothermic. The NaBH4-based composite starts desorbing hydrogen at 240 °C. Its ball milled LiBH4-based counterpart starts desorbing at 200 °C. The latter initially desorbs hydrogen rapidly but then the rate of desorption suddenly decelerates. The estimated apparent activation energy for the NaBH4-based composite without and with n-Ni is equal to 152 ± 2.2 and 157 ± 0.9 kJ/mol, respectively. In contrast, the apparent activation energy for the initial rapid dehydrogenation for the LiBH4-based composite is very low being equal to 47 ± 2 and 38 ± 9 kJ/mol for the composite without and with the n-Ni additive, respectively. XRD phase studies after volumetric isothermal dehydrogenation tests show the presence of NaBO2 and MgO for the NaBH4-based composite. For the LiBH4-based composite phases such as MgO, Li3BO3, MgB2, MgB6 are the products of the first exothermic reaction which has a theoretical H2 capacity of 8.1 wt.%. However, for reasons which are not quite clear, the first reaction never goes to full completion even at 300 °C desorbing ∼4.5 wt.% H2 at this temperature. The products of the second endothermic reaction for the LiBH4-based composite are MgO, MgB6, B and LiMgBO3 and the reaction has a theoretical H2 capacity of 2.26 wt.%. The effect of the addition of 5 wt.% nanometric Ni on the dehydrogenation behavior of both the NaBH4-and LiBH4-based composites is rather negligible. The n-Ni additive may not be the optimal catalyst for these hydride composite systems although more tests are required since only one n-Ni content was examined.  相似文献   

12.
The present investigation describes the hydrogen storage properties of 2:1 molar ratio of MgH2–NaAlH4 composite. De/rehydrogenation study reveals that MgH2–NaAlH4 composite offers beneficial hydrogen storage characteristics as compared to pristine NaAlH4 and MgH2. To investigate the effect of carbon nanostructures (CNS) on the de/rehydrogenation behavior of MgH2–NaAlH4 composite, we have employed 2 wt.% CNS namely, single wall carbon nanotubes (SWCNT) and graphene nano sheets (GNS). It is found that the hydrogen storage behavior of composite gets improved by the addition of 2 wt.% CNS. In particular, catalytic effect of GNS + SWCNT improves the hydrogen storage behavior and cyclability of the composite. De/rehydrogenation experiments performed up to six cycles show loss of 1.50 wt.% and 0.84 wt.% hydrogen capacity in MgH2–NaAlH4 catalyzed with 2 wt.% SWCNT and 2 wt.% GNS respectively. On the other hand, the loss of hydrogen capacity after six rehydrogenation cycles in GNS + SWCNT (1.5 + 0.5) wt.% catalyzed MgH2–NaAlH4 is diminished to 0.45 wt.%.  相似文献   

13.
Nanosized cobalt sulfide and cobalt boride were synthesized and doped into LiBH4 to improve the dehydrogenation properties of this important candidate for hydrogen storage. With respect to CoSx doping, the dehydrogenation temperature (peak temperature observed by mass spectrometry) of pristine LiBH4 can be reduced from 440 °C to 175 °C with a maximum capacity of 6.7 wt% at 50% doping. Unfortunately, B2H6 is liberated and the process is not reversible because the CoSx dopant reacts with LiBH4 to form more stable compounds. By changing CoSx to CoBx, a reversible dehydrogenation was realized with greatly improved reversibility. The dehydrogenation temperature was reduced to 350 °C with a maximum capacity of 8.4 wt% at 50% doping amount. It is very significant that CoBx is stable and the release of B2H6 is eliminated. A reversible hydrogen desorption of about 5.3 wt% can be achieved with a LiBH4 + 50% CoBx mixture under a mild rehydrogenation condition of 400 °C at 10 MPa H2. It is obvious that CoSx acts as a reactant even though the dehydrogenation is greatly enhanced, while CoBx behaves as a catalyst significantly promoting the dehydrogenation and reversibility of LiBH4.  相似文献   

14.
In this work, the hydriding–dehydriding properties of the LiBH4–NbF5 mixtures were investigated. It was found that the dehydrogenation and reversibility properties of LiBH4 were significantly improved by NbF5. Temperature-programed dehydrogenation (TPD) showed that 5LiBH4–NbF5 sample started releasing hydrogen from as low as 60 °C, and 4 wt.% hydrogen could be obtained below 255 °C. Meanwhile, ∼7 wt.% H2 could be reached at 400 °C in 20LiBH4–NbF5 sample, whereas pristine LiBH4 only released ∼0.7 wt.% H2. In addition, reversibility measurement demonstrated that over 4.4 wt.% H2 could still be released even during the fifth dehydrogenation in 20LiBH4–NbF5 sample. The experimental results suggested that a new borohydride possibly formed during ball milling the LiBH4–NbF5 mixtures might be the source of the active effect of NbF5 on LiBH4.  相似文献   

15.
The mutual destabilization of LiAlH4 and MgH2 in the reactive hydride composite LiAlH4-MgH2 is attributed to the formation of intermediate compounds, including Li-Mg and Mg-Al alloys, upon dehydrogenation. TiF3 was doped into the composite for promoting this interaction and thus enhancing the hydrogen sorption properties. Experimental analysis on the LiAlH4-MgH2-TiF3 composite was performed via temperature-programmed desorption (TPD), differential scanning calorimetry (DSC), isothermal sorption, pressure-composition isotherms (PCI), and powder X-ray diffraction (XRD). For LiAlH4-MgH2-TiF3 composite (mole ratio 1:1:0.05), the dehydrogenation temperature range starts from about 60 °C, which is 100 °C lower than for LiAlH4-MgH2. At 300 °C, the LiAlH4-MgH2-TiF3 composite can desorb 2.48 wt% hydrogen in 10 min during its second stage dehydrogenation, corresponding to the decomposition of MgH2. In contrast, 20 min was required for the LiAlH4-MgH2 sample to release so much hydrogen capacity under the same conditions. The hydrogen absorption properties of the LiAlH4-MgH2-TiF3 composite were also improved significantly as compared to the LiAlH4-MgH2 composite. A hydrogen absorption capacity of 2.68 wt% under 300 °C and 20 atm H2 pressure was reached after 5 min in the LiAlH4-MgH2-TiF3 composite, which is larger than that of LiAlH4-MgH2 (1.75 wt%). XRD results show that the MgH2 and LiH were reformed after rehydrogenation.  相似文献   

16.
We have designed a new synthesis method for the ternary metal hydride Mg2FeH6 based on the direct reaction of simple hydrides under high-pressure conditions. Well-crystallized samples were prepared in a piston-cylinder hydrostatic press at 2 GPa and temperatures around 750 °C from mixtures of MgH2 and Fe enclosed in gold or platinum capsules. Seven different samples have been prepared under different conditions. X-ray powder diffraction analysis was used to identify and assess the purity of the samples, through Rietveld analyses of the crystal structure (K2PtCl6-type). Mg2FeH6 shows a cubic symmetry with space group Fm-3m. SEM images show an average particle size of 1–2 μm for Mg2FeH6; the microcrystals present well-grown faces and display a high homogeneity of shapes and sizes. Thermogravimetric analysis has been carried out to determine not only the hydrogen desorption temperature but also the hydrogen contents.  相似文献   

17.
In the present study, the synthesis of two different LiBH4–Y(BH4)3 and LiBH4–YH3 composites was performed by mechanochemical processing of the 4LiBH4–YCl3 mixture and as-milled 4LiBH4–YCl3 plus 3LiH. It was found that Y(BH4)3 and YH3 formed in situ during milling are effective to promote LiBH4 destabilization but differ substantially from each other in terms of the dehydrogenation pathway. During LiBH4–Y(BH4)3 dehydriding, Y(BH4)3 decomposes first generating in situ freshly YH3 and subsequently, it destabilizes LiBH4 with the formation of minor amounts of YB4. About 20% of the theoretical hydrogen storage was obtained via the rehydriding of YB4–4LiH–3LiCl at 400 °C and 6.5 MPa. As a novel result, a compound containing (B12H12)2− group was identified during dehydriding of Y(BH4)3. In the case of 4LiBH4–YH3 dehydrogenation, the increase of the hydrogen back pressure favors the formation of crystalline YB4, whereas a reduction to ≤0.1 MPa induces the formation of minor amounts of Li2B12H12. Although for hydrogen pressures ≤0.1 MPa direct LiBH4 decomposition can occur, the main dehydriding pathway of 4LiBH4–YH3 composite yields YB4 and LiH. The nanostructured composite obtained by mechanochemical processing gives good hydrogen storage reversibility (about 80%) regardless of the hydrogen back pressure.  相似文献   

18.
Sodium aluminum hydride (NaAlH4) was directly synthesized by ball milling NaH/Al co-doped with CeCl3 + KH under a hydrogen pressure of 3 MPa at room temperature. Out of various samples corresponding to xNaH/Al + 0.02CeCl3 + yKH (x + y = 1; y = 0, 0.02, 0.04 mol%) composites, the composite with y = 0.02 exhibits the optimum de/hydrogenation properties. It shows that the addition of KH can effectively improve the dehydrogenation properties of second step reaction of NaAIH4 system. The composite with y = 0.02 starts to release hydrogen from 87 °C and completes dehydrogenation within 20 min at 170 °C, with good cycling de/hydrogenation kinetics at relatively lower temperature (100–140 °C). After ball milling, the CeCl3 precursor can be changed into CeH2 catalytic active component in the first several de/hydrogenation cycles. Apparent activation energy of the second decomposition step of NaAIH4 system can be effectively decreased by addition of KH, resulting in the decrease of desorption temperatures. Based on the microstructure analyses combined with hydrogen storage performances, the improved dehydrogenation properties of sodium aluminum hydride system are ascribed to the lattice volume expansion of Na3AlH6 during the dehydrogenation process resulted from the addition of KH. Moreover, by analyzing the reaction kinetics of CeCl3 + KH co-doped sample, both of the decomposition steps of composite with y = 0.02 were conformed to the two-dimension phase-boundary growth mechanism. The mechanistic investigations gained here could help to understand the de/rehydrogenation behaviors of catalyzed complex metal hydride systems.  相似文献   

19.
A 2LiBH4–MgH2–MoS2 composite was prepared by solid-state ball milling, and the effects of MoS2 as an additive on the hydrogen storage properties of 2LiBH4–MgH2 system together with the corresponding mechanism were investigated. As shown in the TG–DSC and MS results, with the addition of 20 wt.% of MoS2, the onset dehydrogenation temperature is reduced to 206 °C, which is 113 °C lower than that of the pristine 2LiBH4–MgH2 system. Meanwhile, the total dehydrogenation amount can be increased from 9.26 wt.% to 10.47 wt.%, and no gas impurities such as B2H6 and H2S are released. Furthermore, MoS2 improves the dehydrogenation kinetics, and lowers the activation energy (Ea) 34.49 kJ mol−1 of the dehydrogenation reaction between Mg and LiBH4 to a value lower than that of the pristine 2LiBH4–MgH2 sample. According to the XRD test, Li2S and MoB2 are formed by the reaction between LiBH4 and MoS2, which act as catalysts and are responsible for the improved hydrogen storage properties of the 2LiBH4–MgH2 system.  相似文献   

20.
To improve the hydrogen storage property of LiBH4, the LiBH4/Ca(AlH4)2 reactive systems with various ratios were constructed, and their de-/hydrogenation properties as well as the reaction mechanisms were investigated experimentally. It was found that the sample with the LiBH4 to Ca(AlH4)2 molar ratio of 6:1 exhibits the best comprehensive hydrogen storage properties, desorbing hydrogen completely (8.2 wt.%) within 35 min at 450 °C and reversibly absorbing 4.5 wt.% of hydrogen at 450 °C under a hydrogen pressure as low as 4.0 MPa. During the first dehydrogenation process of the LiBH4/Ca(AlH4)2 systems, the CaH2 and Al particles were in situ precipitated via the self-decomposition of Ca(AlH4)2, and then reacted with LiBH4 to form CaB6, AlB2 and LiH. Whereafter, the sample can cycle between LiBH4 + Ca(BH4)2 + Al in the hydrogenated state and CaB6 + AlB2 + LiH in the dehydrogenated state.  相似文献   

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