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1.
The investigation of thermally induced dehydrogenation of LiBH4 reveals that LiBH4 doped with the graphene catalysts shows superior dehydrogenation and rehydrogenation performance to that of Vulcan XC-72, carbon nanotube and BP2000 doped LiBH4. For doping with 20 wt.% graphene, thermal dehydrogenation of LiBH4 is found to start at ca. 230 °C and a total weight loss of 11.4 wt.% can be obtained below 700 °C. With increased loading of graphene within a LiBH4 sample, the onset dehydrogenation temperature and the two main desorption peaks from LiBH4 are found to decrease while the hydrogen release amount is found to increase. Moreover, variation of the equilibrium pressure obtained from isotherms measured at 350–450 °C indicate the dehydrogenation enthalpy is reduced from 74 kJ mol−1 H2 for pure LiBH4 to ca. 40 kJ mol−1 H2 for 20 wt.% graphene doped LiBH4. Importantly, the reversible dehydrogenation/rehydrogenation process was achieved under 3 MPa H2 at 400 °C for 10 h, with a capacity of ca. 4.0 wt.% in the tenth cycle. Especially, LiBH4 is reformed and new species, Li2B10H10, is detected after the rehydrogenation process.  相似文献   

2.
De/rehydrogenation kinetics and reversibility of MgH2 are improved by doping with activated carbon nanofibers (ACNF) and compositing with LiBH4. Via doping with 5 wt % ACNF, hydrogen absorption of Mg to MgH2 (T = 320 °C and p(H2) = 50 bar) increases from 0.3 to 4.5 wt % H2. Significant reduction of onset dehydrogenation temperature of MgH2 to 340 °C (ΔT = 70 °C as compared with pristine MgH2) together with 6.8–8.2 wt % H2 can be obtained by compositing Mg-5 wt. % ACNF with LiBH4 (LiBH4:Mg mole ratios of 0.5:1, 1:1, and 2:1). During dehydrogenation of Mg-rich composites (0.5:1 and 1:1 mol ratios), the formation of MgB2 and Mg0.816Li0.184 implying the reaction between LiBH4 and MgH2 favors kinetic properties and reversibility, while the composite with 2:1 mol ratio shows individual dehydrogenation of LiBH4 and MgH2. For up-scaling to hydrogen storage tank (~120 times greater sample weight than laboratory scale) of the most suitable composite (1:1 mol ratio), de/rehydrogenation kinetics and hydrogen content released at all positions of the tank are comparable and approach to those from laboratory scale. Due to high purity (100%) and temperature of hydrogen gas from hydride tank, the performance of single proton exchange membrane fuel cell enhances up to 30% with respect to the results from compressed gas tank.  相似文献   

3.
The effect of nanoscale h-BN addition by milling on the de-/re-hydrogenation of LiBH4 was investigated. With the increasing h-BN ratio, the milled LiBH4/h-BN composites showed lower dehydrogenation temperature. For the LiBH4-3BN composite (mole ratio 1:3), the on-set dehydrogenation temperature was reduced from 290 °C for the milled pure LiBH4 down to 175 °C, and the initial dehydrogenation capacity could reach 3.1 wt.% (equivalent to 13.7 wt.% of the component LiBH4) within ~2 h at 400 °C. Under moderate rehydrogenation conditions of 400 °C and 10 MPa H2 pressure, the 2nd and 3th cyclic dehydrogenation capacity of LiBH4-3BN composite almost remained unchanged, indicating remarkably improved rehydrogenation reversibility in comparison to milled pure LiBH4. FTIR analysis reveals specific interaction between h-BN and LiBH4 probably originating from the polar mechanism between polarizable B–H bond and B–N bond, which should be responsible for the enhanced dehydrogenation kinetics and reversibility. This work demonstrates the specific catalytic role of nanoscale h-BN and its potential for reversible hydrogen storage by compositing with high-capacity borohydrides.  相似文献   

4.
To improve the packing efficiency in tank scale, hydrides have been compacted into pellet form; however, poor hydrogen permeability through the pellets results in sluggish kinetics. In this work, the hydrogen sorption properties of compacted 2LiBH4MgH2 doped with 30 wt % activated carbon nanofibers (ACNF) are investigated. After doping with ACNF, onset dehydrogenation temperature of compacted 2LiBH4MgH2 decreases from 350 to 300 °C and hydrogen released content enhances from 55 to 87% of the theoretical capacity. The sample containing ACNF releases hydrogen following a two-step mechanism with reversible hydrogen storage capacities up to 4.5 wt % H2 and 41.8 gH2/L, whereas the sample without ACNF shows a single-step decomposition mainly from MgH2 with only 1.8 wt % H2 and 15.4 gH2/L. Significant kinetic improvement observed in the doped system is due to the enhancement of both hydrogen permeability and heat transfer through the pellet.  相似文献   

5.
Though LiBH4-MgH2 system exhibits an excellent hydrogen storage property, it still presents high decomposition temperature over 350 °C and sluggish hydrogen absorption/desorption kinetics. In order to improve the hydrogen storage properties, the influence of MoCl3 as an additive on the hydrogenation and dehydrogenation properties of LiBH4-MgH2 system is investigated. The reversible hydrogen storage performance is significantly improved, which leads to a capacity of about 7 wt.% hydrogen at 300 °C. XRD analysis reveals that the metallic Mo is formed by the reaction between LiBH4 and MoCl3, which is highly dispersed in the sample and results in improved dehydrogenation and hydrogenation performance of LiBH4-MgH2 system. From Kissinger plot, the activation energy for hydrogen desorption of LiBH4-MgH2 system with additive MoCl3 is estimated to be ∼43 kJ mol−1 H2, 10 kJ mol−1 lower than that for the pure LiBH4-MgH2 system indicating that the kinetics of LiBH4-MgH2 composite is significantly improved by the introduction of Mo.  相似文献   

6.
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   

7.
The de-/rehydrogenation features of the 6LiBH4/SrF2 reactive hydride system have been systematically investigated. It was found that the thermal stability of LiBH4 can be reduced markedly by combining it with SrF2. Dehydrogenation of the 6LiBH4/SrF2 system proceeds via the 6LiBH4 + SrF2 → SrB6 + 2LiF + 4LiH + 10H2 reaction, which involves SrH2 as the intermediate product. The dehydrogenation enthalpy change was experimentally determined to be 52 kJ/mol H2 based on the P–C isotherm analysis. For rehydrogenation, LiBH4 and SrF2 were regenerated along with LiSrH3 at 450 °C under ~8 MPa hydrogen pressure; thus, approximately 5.2 wt% of hydrogen can be released during the second dehydrogenation process.  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.
De/rehydrogenation performances and reaction pathways of nanoconfined 2LiBH4MgH2 into activated carbon (AC) packed in small hydrogen storage tank are proposed for the first time. Total and material storage capacities upon five hydrogen release and uptake cycles are 3.56–4.55 and 2.03–3.28 wt % H2, respectively. Inferior hydrogen content to theoretical capacity (material capacity of 5.7 wt % H2) is due to partial dehydrogenation during sample preparation and incomplete decomposition of LiBH4 as well as the formation of thermally stable Li2B12H12 upon cycling. Two-step dehydrogenation of MgH2 and LiBH4 to produce Mg and MgB2+LiH, respectively is found at all positions in the tank. For rehydrogenation, reversibility of MgH2 and LiBH4 proceeds via different reaction mechanisms. Although isothermal condition (Tset = 350 °C) and controlled pressure range (e.g., 30–40 bar H2 for hydrogenation) are applied, temperature gradient inside the tank and poor hydrogen diffusion through hydride bed, especially in the sample bulk are detected. This results in alteration of de/rehydrogenation pathways of hydrides at different positions in the tank. Thus, further development of hydrogen storage tank based 2LiBH4MgH2 nanoconfined in AC includes the improvement of thermal conductivity of materials and temperature control system as well as hydrogen permeability.  相似文献   

10.
By doping with 5 wt % TiF4 and activated carbon (AC), onset and main dehydrogenation temperatures of MgH2 significantly reduce (ΔT = 138 and 109 °C, respectively) with hydrogen capacity of 4.4 wt % H2. Up-scaling to storage tank begins with packing volume and sample weight of 28.8 mL and ~14.5 g, respectively, and continues to 92.6 mL and ~60.5–67 g, respectively. Detailed hydrogen sorption mechanisms and kinetics of the tank tightly packed with four beds of MgH2TiF4-AC (~60.5 g) are investigated. De/rehydrogenation mechanisms are detected by three temperature sensors located at different positions along the tank radius, while hydrogen permeability is benefited by stainless steel mesh sheets and tube inserted in the hydride beds. Fast desorption kinetics of MgH2TiF4-AC tank at ~275–283 °C, approaching to onset dehydrogenation temperature of the powder sample (272 °C) suggests comparable performances of laboratory and tank scales. Hydrogen desorption (T = 300 °C and P(H2) = 1 bar) and absorption (T = 250 °C and P(H2) = 10–15 bar) of MgH2TiF4-AC tank provide gravimetric and volumetric capacities during the 1st-2nd cycles of 4.46 wt % H2 and 28 gH2/L, respectively, while those during the 3rd-15th cycles are up to 3.62 wt % H2 and 23 gH2/L, respectively. Due to homogeneous heat transfer along the tank radius, de/rehydrogenation kinetics superior at the tank center and degrading forward the tank wall can be due to poor hydrogen permeability. Particle sintering and/or agglomeration upon cycling yield deficient hydrogen content reproduced.  相似文献   

11.
The hydrogen storage properties of 5LiBH4 + Mg2FeH6 reactive hydride composites for reversible hydrogen storage were investigated by comparing with the 2LiBH4 + MgH2 composite in the present work. The dehydrogenation pathway and reaction mechanism of 5LiBH4 + Mg2FeH6 composite were also investigated and elucidated. The self-decomposition of Mg2FeH6 leads to the in situ formation of Mg and Fe particles on the surface of LiBH4, resulting in a well dispersion between different reacting phases. The formation of FeB is observed during the dehydrogenation of 5LiBH4 + Mg2FeH6 composite, which might supplies nucleation sites of MgB2 during the dehydrogenation process, but is not an ascendant catalyst for the self-decomposition of LiBH4. And FeB can also transform to the LiBH4 and Fe by reacting with LiH and H2 during the rehydrogenation process. The dehydrogenation capacity for 5LiBH4 + Mg2FeH6 composite still gets to 6.5 wt% even after four cycles. The X-ray diffraction analyses reveal the phase transitions during the hydriding and dehydriding cycle. The formed FeB in the composite maintains a nanostructure after four hydriding-dehydriding cycles. The loss of hydrogen storage capacity and de-/rehydrogenation kinetics can be attributed to the incomplete generation of Mg2FeH6 during the rehydrogenation process.  相似文献   

12.
This work highlights the dehydrogenation mechanisms of a 0.62LiBH4–0.38NaBH4 mixture in the range of 25–650 °C in flowing Ar. The dehydrogenation starts from 287 °C followed by two decomposition steps at 488 °C and 540 °C. These peak temperatures are in the range of 470 °C (for pure LiBH4)–580 °C (for pure NaBH4) due to different Pauling electronegativity values for Li+ (0.98) and Na+ (0.93) that affects the stability and decomposition temperatures. The 1st step of dehydrogenation is accompanied with precipitation of LiH, Li2B12H12 and B in between 287 and 520 °C; whilst the 2nd step of dehydrogenation is mainly accompanied by the precipitation of Na and B when temperature is higher than 520 °C. The total amount of H2 released is 10.8 wt.% that exceeds the estimated amount (8.9 wt.%), indicating less metal dodecaborate (than that for pure LiBH4) is formed during the decomposition.  相似文献   

13.
In this report, Ni and TiO2 are successfully embedded into porous carbon aerogel (CA) (donated as NiTiO2@CA). Meanwhile, the synergistic effect of Ni, TiO2 and CA on the dehydrogenation properties of LiBH4 is systematically studied. Ni@CA, TiO2@CA and CA are also investigated for comparisons. Compared to other three materials, NiTiO2@CA exhibits better performance when used as a carrier to support LiBH4. More than 6.75 wt% H2 is released from LiBH4NiTiO2@CA system in nearly 120 min at 350 °C, exhibiting a higher dehydrogenation capacity than that of LiBH4Ni@CA (3.15 wt %), LiBH4TiO2@CA (5.15 wt%) and LiBH4-CA (2.05 wt %), respectively. Furthermore, the apparent energy (Ea) calculated with Kissinger method is 118.8 kJ/mol, much lower than that of pure LiBH4. Dehydrogenation performance of LiBH4NiTiO2@CA may be due to the synergetic effect of destabilization of TiO2, catalysis of Ni, as well as the nanoconfinement of CA.  相似文献   

14.
LiBH4 is a promising hydrogen storage material for its large capacity. However, high desorption temperature, sluggish kinetics and demanding rehydrogenation severely hinder its practical use. Surface functional groups of graphene in many cases are treated as effective approaches to obtain some kinds of excellent properties of energy storage materials. In the current work, a new facile and effective strategy to improve the reversible hydrogen desorption properties of LiBH4 is proposed by composing with functionalized graphene to form the LiBH4–fluorographene composite. The fluorographene (FG) nanosheets are successfully exfoliated from fluorographite (FGi) and composed with LiBH4. It is demonstrated that the FG can remarkably improve the hydrogen desorption thermodynamics, kinetics and reversibility of LiBH4 via reactant destabilization method. An extremely fast hydrogen desorption process with a high capacity of 8.2 wt.% at 148.1 °C is achieved in the LiBH4–50FG composite. Further research reveals that the enhancement actually roots in the strengthened interfacial interaction between LiBH4 and exfoliated FG. Moreover, it is confirmed that the LiBH4–40FG composite exhibits a significantly enhanced reversible hydrogen desorption capacity of 7.2 wt.% and LiBH4 is regenerated. Such enhanced reversible hydrogen desorption properties are ascribed to the strengthened interfacial interactions between LiBH4 and FG with large surface, as well as the formation of LiHxF1?x phase.  相似文献   

15.
LiBH4 has a high hydrogen storage capacity and could potentially serve as a superior hydrogen storage material. However, during the hydrolysis process for hydrogen generation, the agglomeration of the hydrolysis product of LiBH4 limits its full utilization. In order to completely release the stoichiometric amount of H2 from LiBH4 hydrolysis, multiwalled carbon nanotubes (MWCNTs) were doped with LiBH4 by mechanical milling. The results show that MWCNT carried LiBH4 can slowly react with water vapor at room temperature which is 25 °C lower than the reaction temperature of neat LiBH4. Agglomeration can be avoided when the addition of MWCNTs exceeds 7 wt.%, which results in a complete hydrolysis process. The total hydrogen capacity is 7.5 wt.%. The enhanced hydrolysis of LiBH4 can be attributed to the MWCNTs which increased the contact areas between LiBH4 and water and created gas channels for hydrogen diffusion. The performance of a micro proton exchange membrane fuel cell connected to MWCNT-doped LiBH4 powder packed-bed reactor was examined. The result demonstrates that doping with MWCNTs enhanced the hydrogen generation of LiBH4 hydrolysis. MWCNT-doped LiBH4 can be applied as hydrogen source of fuel cells.  相似文献   

16.
The formation of metastable γ-MgH2 upon application of ultra-high pressure and its dehydrogenation properties were studied. Magnesium-nickel alloy (14 wt.% Ni) was hydrogenated and compressed at ultra-high pressures of 2.5 and 4 GPa. The phase composition and desorption properties of the products were investigated. Powder X-ray diffraction indicated that some α-MgH2 converted to γ-MgH2 during compression. This resulted in the onset of hydrogen desorption at 60 °C under vacuum. Our findings thus show that application of ultra-high pressure can facilitate the formation of γ-MgH2, which has a lower dehydrogenation temperature (≤200 °C) than α-MgH2, which desorbs at temperatures above 300 °C. The metastable phase possessed a high hydrogen storage capacity of at least 4.5 wt.%. These properties revealed the potential of γ-MgH2 as a future hydrogen storage material.  相似文献   

17.
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   

18.
The 2LiBH4–MgH2 reactive hydride composite is a promising hydrogen storage system due to the combined high hydrogen capacity and relatively moderate reaction enthalpy. However, the sluggish de/rehydrogenation kinetics severely impedes its practical applications. In this study, graphitic carbon nitride (C3N4) as a metal-free additive was added to the 2LiBH4–MgH2 composite and examined with respect to the promoting effect on the hydrogen storage properties of the composite. Our study found that mechanically milling with small amount of C3N4 additive can eliminate the incubation period between two dehydrogenation steps and thus markedly enhance the dehydrogenation kinetics of the LiBH4–MgH2 composite. Further cyclic study found that the composite with C3N4 additive exhibits improved cyclic dehydrogenation property although it also shows capacity loss upon cycling, particularly in the second cycle. Combined dehydrogenation property, phase analysis and a series of designed experiments suggested that the C3N4 additive could react with both LiBH4 and MgH2 in heating process, and the resulting products may improve the reversible dehydrogenation property of the composite system.  相似文献   

19.
The suitable thermodynamics and sorption properties of 2LiBH4-MgH2 system inspired us to explore the effect of KH on this system. The addition of 5 mol% KH to this system didn't show any significant effect on desorption temperature, however, an interesting peak shift to lower temperature was observed that corresponds to the melting of 2LiBH4-MgH2. This gave us a sign of eutectic phenomenon that has been observed in 2LiBH4-KBH4 system recently. To explore it in more detail, a series of (2LiBH4-MgH2)x-(KH)1-x system was examined and a pseudo-binary phase diagram for this system has been plotted. Using this phase diagram, the eutectic composition has been identified for x = 0.45 with the lowest melting temperature at 79 °C.  相似文献   

20.
CeF3 as a catalyst is first added to activated carbon (AC) by ball milling under low rotation speed. Then the treated AC was used as the scaffold to confine LiBH4 by melt infiltration process. The combined effects of confinement and CeF3 doping on the hydrogen storage properties of LiBH4 are studied. The experimental results show that LiBH4 and CeF3 are well dispersed in the AC scaffold and occupy up to 90% of the pores of AC. Compared with pristine LiBH4, the onset dehydrogenation temperature for LiBH4-AC and LiBH4-AC-CeF3 decreases by 150 and 190 °C, respectively. And the corresponding dehydrogenation capacity increases from 8.2 wt% to 13.1 wt% for LiBH4-AC and 12.8 wt% for LiBH4-AC-CeF3, respectively. The maximum dehydrogenation speed of LiBH4-AC and LiBH4-AC-CeF3 is 80 and 288 times higher than that of pristine LiBH4 at 350 °C. And LiBH4-AC andLiBH4-AC-CeF3 show good reversible hydrogen storage properties. On the during 4th dehydrogenation cycle, the hydrogen release capacity of LiBH4-AC and LiBH4-AC-5 wt% CeF3 reaches 8.1 and 9.3 wt%, respectively.  相似文献   

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