ABSTRACT
Lithium hydride (LiH), a saline hydride with a hydrogen density of 12.6 wt %, is highly thermostable, which hinders its extensive application in hydrogen storage. In this study, we demonstrate a distinct photodecomposition of LiH under ambient conditions. Ultraviolet-visible (UV-vis) illumination induces hydrogen release and creates surface hydrogen vacancies on LiH. The subsequent H- migration enables hydrogen desorption and the accumulation of vacancies at the subsurface, resulting in the generation of metallic Li clusters. Rehydrogenation, on the contrary, can be charged under UV-vis illumination in 1 bar H2. Such phenomena show that the thermodynamic and kinetic limits in the re/dehydrogenation of LiH can be broken under illumination, which allows hydrogen storage over the LiH surface at temperatures â¼600 K lower than those of the corresponding thermal process. This work provides new insights into the interaction of semiconducting hydrides and photons and opens an avenue for the development and optimization of materials for hydrogen storage and related photodriven reactions.
ABSTRACT
Mixed solid solutions have played an important role in improving the kinetics and performance of hydrogen storage materials, as reported for the Li-Mg-N-H, K-Mg-N-H, and Rb-Mg-N-H systems. Besides, the formation of a homogeneous solid solution, mostly due to partial ionic substitution, is known to be an effective approach to improve the ionic conductivity of a material, which is an important property in electrochemical applications. We have reported a series of solid solutions based on mixed amide-hydride materials of the Group 1 elements, e.g., K(NH2)xH1-x, Rb(NH2)xH1-x, and Cs(NH2)xH1-x, via the exchange of NH2-/H- anions with the change of the lattice cell of the solid solution. Extending the research in this direction, we study the M-N-H solid solution in the MNH2-MH systems (M = K, Rb, Cs, and their combinations), i.e., KNH2-RbH, RbNH2-KH, RbNH2-CsH, and CsNH2-RbH via ex situ/in situ XRD, IR, and 1H 2D solid-state NMR. The results obtained confirm the formation of mixed metal amide-hydride solid solutions associated with an exchange between both anionic (NH2- and H-) and cationic species (K+, Rb+, and Cs+). With this study, we aim to create an accessible library of M-N-H solid solutions for further studies as additives for hydrogen storage materials or ionic conductors.
ABSTRACT
The reactive hydride composite (RHC) LiBH4-MgH2 is regarded as one of the most promising materials for hydrogen storage. Its extensive application is so far limited by its poor dehydrogenation kinetics, due to the hampered nucleation and growth process of MgB2. Nevertheless, the poor kinetics can be improved by additives. This work studied the growth process of MgB2 with varying contents of 3TiCl3·AlCl3 as an additive, and combined kinetic measurements, X-ray diffraction (XRD), and advanced transmission electron microscopy (TEM) to develop a structural understanding. It was found that the formation of MgB2 preferentially occurs on TiB2 nanoparticles. The major reason for this is that the elastic strain energy density can be reduced to ~4.7 × 107 J/m3 by creating an interface between MgB2 and TiB2, as opposed to ~2.9 × 108 J/m3 at the original interface between MgB2 and Mg. The kinetics of the MgB2 growth was modeled by the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation, describing the kinetics better than other kinetic models. It is suggested that the MgB2 growth rate-controlling step is changed from interface- to diffusion-controlled when the nucleation center changes from Mg to TiB2. This transition is also reflected in the change of the MgB2 morphology from bar- to platelet-like. Based on our observations, we suggest that an additive content between 2.5 and 5 mol% 3TiCl3·AlCl3 results in the best enhancement of the dehydrogenation kinetics.
ABSTRACT
The hampered kinetics of reactive hydride composites (RHCs) in hydrogen storage and release, which limits their use for extensive applications in hydrogen storage S1and energy conversion, can be improved using additives. However, the mechanism of the kinetic restriction and the additive effect on promoting the kinetics have remained unclear. These uncertainties are addressed by utilizing versatile transmission electron microscopy (TEM) on the LiBH4-MgH2 composite under the influence of the 3TiCl3·AlCl3 additives. The formation of the MgB2 phase, as the rate-limiting step, is emphatically studied. According to the observations, the heterogeneous nucleation of MgB2 relies on different nucleation centers (Mg or TiB2 and AlB2). The varied nucleation and growth of MgB2 are related to the in-plane strain energy density at the interface, resulting from the atomic misfit between MgB2 and its nucleation centers. This leads to distinct MgB2 morphologies (bars and platelets) and different performances in the dehydrogenation kinetics of LiBH4-MgH2. It was found that the formation of numerous MgB2 platelets is regarded as the origin of the kinetic improvement. Therefore, to promote dehydrogenation kinetics in comparable RHC systems for hydrogen storage, it is suggested to select additives delivering a small atomic misfit.
ABSTRACT
Reversible solid-state hydrogen storage is one of the key technologies toward pollutant-free and sustainable energy conversion. The composite system LiBH4-MgH2 can reversibly store hydrogen with a gravimetric capacity of 13 wt%. However, its dehydrogenation/hydrogenation kinetics is extremely sluggish (â¼40 h) which hinders its usage for commercial applications. In this work, the kinetics of this composite system is significantly enhanced (â¼96%) by adding a small amount of NbF5. The catalytic effect of NbF5 on the dehydrogenation/hydrogenation process of LiBH4-MgH2 is systematically investigated using a broad range of experimental techniques such as in situ synchrotron radiation X-ray powder diffraction (in situ SR-XPD), X-ray absorption spectroscopy (XAS), anomalous small angle X-ray scattering (ASAXS), and ultra/small-angle neutron scattering (USANS/SANS). The obtained results are utilized to develop a model that explains the catalytic function of NbF5 in hydrogen release and uptake in the LiBH4-MgH2 composite system.
ABSTRACT
Due to the considerable interest in vanadium niobium oxides as a lithium storage material, the kinetics and transformation processes of the V2O5-5Nb2O5 system have been investigated by in situ synchrotron powder X-ray diffraction. The diffraction data after the thermal treatments selected with a view on the most significant features were supplemented with specific ex situ experiments conducted using a laboratory rotating anode X-ray diffractometer. The morphological changes of the mixed powders assuming an amorphous and nanocrystalline solid solution structure as a function of the temperature were inspected by scanning electron microscopy observations. The structural solution of the powder diffraction pattern of the phase recorded in situ at a temperature of about 700 °C was compatible with an orthorhombic crystal structure with the space group Amm2. The obtained lattice parameters for this structure were a = 3.965 Å; b = 17.395 Å, c = 17.742 Å, and the cell composition was V4Nb20O60, Pearson symbol oA84, and density = 4.10 g cm-3. In this structure, while the niobium atoms may be four-, five-, and six-fold coordinated by oxygen atoms, the vanadium atoms were six-fold or seven-fold coordinated. At the temperature of 800 °C and just above, the selected 1 : 2 and 1 : 3 V2O5-Nb2O5 compositions, respectively, returned mostly a tetragonal VNb9O25 phase, in line with earlier observations conducted for determination of the stability phase diagram of such quasi-binary systems.
ABSTRACT
There are several techniques providing quantitative elemental analysis, but very few capable of identifying both the concentration and chemical state of elements. This study presents a systematic investigation of the properties of the X-rays emitted after the atomic capture of negatively charged muons. The probability rates of the muonic transitions possess sensitivity to the electronic structure of materials, thus making the muonic X-ray Emission Spectroscopy complementary to the X-ray Absorption and Emission techniques for the study of the chemistry of elements, and able of unparalleled analysis in case of elements bearing low atomic numbers. This qualitative method is applied to the characterization of light elements-based, energy-relevant materials involved in the reaction of hydrogen desorption from the reactive hydride composite Ca(BH4)2-Mg2NiH4. The origin of the influence of the band-structure on the muonic atom is discussed and the observed effects are attributed to the contribution of the electronic structure to the screening and to the momentum distribution in the muon cascade.
ABSTRACT
Rechargeable solid-state magnesium batteries are considered for high energy density storage and usage in mobile applications as well as to store energy from intermittent energy sources, triggering intense research for suitable electrode and electrolyte materials. Recently, magnesium borohydride, Mg(BH4)2, was found to be an effective precursor for solid-state Mg-ion conductors. During the mechanochemical synthesis of these Mg-ion conductors, amorphous Mg(BH4)2 is typically formed and it was postulated that this amorphous phase promotes the conductivity. Here, electrochemical impedance spectroscopy of as-received γ-Mg(BH4)2 and ball milled, amorphous Mg(BH4)2 confirmed that the conductivity of the latter is ~2 orders of magnitude higher than in as-received γ-Mg(BH4)2 at 353 K. Pair distribution function (PDF) analysis of the local structure shows striking similarities up to a length scale of 5.1 Å, suggesting similar conduction pathways in both the crystalline and amorphous sample. Up to 12.27 Å the PDF indicates that a 3D net of interpenetrating channels might still be present in the amorphous phase although less ordered compared to the as-received γ-phase. However, quasi elastic neutron scattering experiments (QENS) were used to study the rotational mobility of the [BH4] units, revealing a much larger fraction of activated [BH4] rotations in amorphous Mg(BH4)2. These findings suggest that the conduction process in amorphous Mg(BH4)2 is supported by stronger rotational mobility, which is proposed to be the so-called "paddle-wheel" mechanism.
ABSTRACT
In this work, the possibility of creating a polymer-based adaptive scaffold for improving the hydrogen storage properties of the system 2LiH+MgB2+7.5(3TiCl3·AlCl3) was studied. Because of its chemical stability toward the hydrogen storage material, poly(4-methyl-1-pentene) or in-short TPXTM was chosen as the candidate for the scaffolding structure. The composite system was obtained after ball milling of 2LiH+MgB2+7.5(3TiCl3·AlCl3) and a solution of TPXTM in cyclohexane. The investigations carried out over the span of ten hydrogenation/de-hydrogenation cycles indicate that the material containing TPXTM possesses a higher degree of hydrogen storage stability.
ABSTRACT
The system Mg(NH2)2 + 2LiH is considered as an interesting solid-state hydrogen storage material owing to its low thermodynamic stability of ca. 40 kJ/mol H2 and high gravimetric hydrogen capacity of 5.6 wt.%. However, high kinetic barriers lead to slow absorption/desorption rates even at relatively high temperatures (>180 °C). In this work, we investigate the effects of the addition of K-modified LixTiyOz on the absorption/desorption behaviour of the Mg(NH2)2 + 2LiH system. In comparison with the pristine Mg(NH2)2 + 2LiH, the system containing a tiny amount of nanostructured K-modified LixTiyOz shows enhanced absorption/desorption behaviour. The doped material presents a sensibly reduced (â¼30 °C) desorption onset temperature, notably shorter hydrogen absorption/desorption times and reversible hydrogen capacity of about 3 wt.% H2 upon cycling. Studies on the absorption/desorption processes and micro/nanostructural characterizations of the Mg(NH2)2 + 2LiH + K-modified LixTiyOz system hint to the fact that the presence of in situ formed nanostructure K2TiO3 is the main responsible for the observed improved kinetic behaviour.
ABSTRACT
CO2 emissions have been continuously increasing during the last half of the century with a relevant impact on the planet and are the main contributor to the greenhouse effect and global warming. The development of new technologies to mitigate these emissions poses a challenge. Herein, the recycling of CO2 to produce CH4 selectively by using Mg2FeH6 and Mg2NiH4 complex hydrides as dual conversion promoters and hydrogen sources has been demonstrated. Magnesium-based metal hydrides containing Fe and Ni catalyzed the hydrogenation of CO2 and their total conversion was obtained at 400 °C after 5 h and 10 h, respectively. The complete hydrogenation of CO2 depended on the complex hydride, H2 : CO2 mol ratio, and experimental conditions: temperature and time. For both hydrides, the activation of CO2 on the metal surface and its subsequent capture resulted in the formation of MgO. Investigations on the Mg2FeH6-CO2 system indicated that the main process occurs via the reversed water-gas shift reaction (WGSR), followed by the methanation of CO in the presence of steam. In contrast, the reduction of CO2 by the Mg-based hydride in the Mg2NiH4-CO2 system has a strong contribution to the global process. Complex metal hydrides are promising dual promoter-hydrogen sources for CO2 recycling and conversion into valuable fuels such as CH4.
ABSTRACT
A new and solvent-free synthesis route has been adopted and optimized to prepare crystalline VNbO5 from the mechanochemical reaction between Nb2O5 and V2O5 as starting reagents. The substantially amorphous mixture of equimolar pentoxide V and Nb metals observed after extended mechanical treatment transforms into a crystalline powder following calcination under mild conditions at 710 K. The structure solution of the X-ray diffraction pattern using a global optimization approach, combined with Rietveld refinement, points to a space group P212121 (no. 19) different from Pnma (no. 62) previously proposed in the literature assuming it to be isostructural to VTaO5. The new space group helps to describe weak peaks that remained previously unaccounted for and allows more reliable determination of atomic fractional coordinates and interatomic distance distribution. The as-prepared VNbO5 has been tested as a dopant (5 wt%) for the purpose of solid state hydrogen storage, decreasing significantly the release of hydrogen of MgH2/Mg (620 K) and further enhancing the hydrogen sorption kinetic properties.
ABSTRACT
Binary combinations of borohydrides have been extensivly investigated evidencing the formation of eutectics, bimetallic compounds or solid solutions. In this paper, the investigation has been extended to ternary and quaternary systems in the LiBH4 -NaBH4 -KBH4 -Mg(BH4 )2 -Ca(BH4 )2 system. Possible interactions among borohydrides in equimolar composition has been explored by mechanochemical treatment. The obtained phases were analysed by X-ray diffraction and the thermal behaviour of the mixtures were analysed by HP-DSC and DTA, defining temperature of transitions and decomposition reactions. The release of hydrogen was detected by MS, showing the role of the presence of solid solutions and multi-cation compounds on the hydrogen desorption reactions. The presence of LiBH4 generally promotes the release of H2 at about 200 °C, while KCa(BH4 )3 promotes the release in a single-step reaction at higher temperatures.
ABSTRACT
The crystal structure of a mixed amide-imide phase, RbMgND2ND, has been solved in the orthorhombic space group Pnma ( a = 9.55256(31), b = 3.70772(11) and c = 10.08308(32) Å). A new metal amide-hydride solid solution, Rb(NH2) xH(1- x), has been isolated and characterized in the entire compositional range. The profound analogies, as well as the subtle differences, with the crystal chemistry of KMgND2ND and K(NH2) xH1- x are thoroughly discussed. This approach suggests that the comparable performances obtained using K- and Rb-based additives for the Mg(NH2)2- 2LiH and 2LiN H2-MgH2 hydrogen storage systems are likely to depend on the structural similarities of possible reaction products and intermediates.
ABSTRACT
Complex hydrides have played important roles in energy storage area. Here a complex hydride made of Li2 NH and LiBH4 was synthesized, which has a structure tentatively indexed using an orthorhombic cell with a space group of Pna21 and lattice parameters of a=10.121, b=6.997, and c=11.457â Å. The Li2 NH-LiBH4 sample (in a molar ratio of 1:1) shows excellent hydrogenation kinetics, starting to absorb H2 at 310â K, which is more than 100â K lower than that of pristine Li2 NH. Furthermore, the Li+ ion conductivity of the Li2 NH-LiBH4 sample is about 1.0×10-5 â S cm-1 at room temperature, and is higher than that of either Li2 NH or LiBH4 at 373â K. Those unique properties of the Li2 NH-LiBH4 complex render it a promising candidate for hydrogen storage and Li ion conduction.
ABSTRACT
The 6Mg(NH2)2-9LiH-LiBH4 composite system has a maximum reversible hydrogen content of 4.2 wt% and a predicted dehydrogenation temperature of about 64 °C at 1 bar of H2. However, the existence of severe kinetic barriers precludes the occurrence of de/re-hydrogenation processes at such a low temperature (H. Cao, G. Wu, Y. Zhang, Z. Xiong, J. Qiu and P. Chen, J. Mater. Chem. A, 2014, 2, 15816-15822). In this work, Li3N and YCl3 have been chosen as co-additives for this system. These additives increase the hydrogen storage capacity and hasten the de/re-hydrogenation kinetics: a hydrogen uptake of 4.2 wt% of H2 was achieved in only 8 min under isothermal conditions at 180 °C and 85 bar of H2 pressure. The re-hydrogenation temperature, necessary for a complete absorption process, can be lowered below 90 °C by increasing the H2 pressure above 185 bar. Moreover, the results indicate that the hydrogenation capacity and absorption kinetics can be maintained roughly constant over several cycles. Low operating temperatures, together with fast absorption kinetics and good reversibility, make this system a promising on-board hydrogen storage material. The reasons for the improved de/re-hydrogenation properties are thoroughly investigated and discussed.
ABSTRACT
A new complex ternary amide, Rb2 [Mn(NH2 )4 ], which simultaneously contains both transition and alkali metal catalytic sites, is developed. This is in line with the recently reported TM-LiH composite catalysts, which have been shown to effectively break the scaling relations and achieve ammonia synthesis under mild conditions. Rb2 [Mn(NH2 )4 ] can be facilely synthesized by mechanochemical reaction at room temperature. It exhibits two temperature-dependent polymorphs, that is, a low-temperature orthorhombic and a high-temperature monoclinic structure. Rb2 [Mn(NH2 )4 ] decomposes to N2 , H2 , NH3 , Mn3 N2 , and RbNH2 under inert atmosphere; whereas it releases NH3 at a temperature as low as 80 °C under H2 atmosphere. Those unique behaviors enable Rb2 [Mn(NH2 )4 ], and its analogue K2 [Mn(NH2 )4 ], to be excellent catalytic materials for ammonia decomposition and synthesis. Experimental results show both ammonia decomposition onset temperatures and conversion rates over Rb2 [Mn(NH2 )4 ] and K2 [Mn(NH2 )4 ] are similar to those of noble metal Ru-based catalysts. More importantly, these ternary amides exhibit superior capabilities in catalyzing NH3 synthesis, which are more than 3 orders of magnitude higher than that of Mn nitride and twice of that of Ru/MgO. The in situ SR-PXD measurement shows that manganese nitride, synergistic with Rb/KH or Rb/K(NH2 )x H1-x , are likely the active sites. The chemistry of Rb2 /K2 [Mn(NH2 )x ] and Rb/K(NH2 )x H1-x with H2 /N2 and NH3 correlates closely with the catalytic performance.
ABSTRACT
A series of ammine metal-dodecahydro-closo-dodecaboranes, MxB12H12·nNH3 (M = Li, Na, Ca) were synthesized and their structural and thermal properties studied with in situ time-resolved synchrotron radiation powder X-ray diffraction, thermal analysis, Fourier transformed infrared spectroscopy, and temperature-programmed photographic analysis. The synthesized compounds, Li2B12H12·7NH3, Na2B12H12·4NH3 and CaB12H12·6NH3, contain high amounts of NH3, 43.3, 26.6 and 35.9 wt% NH3, respectively, which can be released and absorbed reversibly at moderate conditions without decomposition, thereby making the closo-boranes favorable 'host' materials for ammonia or indirect hydrogen storage in the solid state. In this work, fifteen new ammine metal dodecahydro-closo-dodecaborane compounds are observed by powder X-ray diffraction, of which six are structurally characterized, Li2B12H12·4NH3, Li2B12H12·2NH3, Na2B12H12·4NH3, Na2B12H12·2NH3, CaB12H12·4NH3 and CaB12H12·3NH3. Li2B12H12·4NH3 and Na2B12H12·4NH3 are isostructural and monoclinic (P21/n) whereas Na2B12H12·2NH3 and CaB12H12·3NH3 are both trigonal with space groups P3[combining macron]m1 and R3[combining macron]c, respectively. Generally, coordination between the metal and the icosahedral closo-borane anion is diverse and includes point sharing, edge sharing, or face sharing, while coordination of ammonia always occurs via the lone pair on nitrogen to the metal. Furthermore, a liquid intermediate is observed during heating of Li2B12H12·7NH3. This work provides deeper insight into the structural, physical, and chemical properties related to thermal decomposition and possible ammonia and hydrogen storage.
ABSTRACT
The hydrogen desorption pathways and storage properties of 2 Mg(NH2 )2 -3 LiH-xLiBH4 samples (x=0, 1, 2, and 4) were investigated systematically by a combination of pressure composition isotherm (PCI), differential scanning calorimetric (DSC), and volumetric release methods. Experimental results showed that the desorption peak temperatures of 2 Mg(NH2 )2 -3 LiH-xLiBH4 samples were approximately 10-15 °C lower than that of 2 Mg(NH2 )2 -3 LiH. The 2 Mg(NH2 )2 -3 LiH-4 LiBH4 composite in particular began to release hydrogen at 90 °C, thereby exhibiting superior dehydrogenation performance. All of the LiBH4 -doped samples could be fully dehydrogenated and re-hydrogenated at a temperature of 143 °C. The high hydrogen pressure region (above 50â bar) of PCI curves for the LiBH4 -doped samples rose as the amount of LiBH4 increased. LiBH4 changed the desorption pathway of the 2 Mg(NH2 )2 -3 LiH sample under a hydrogen pressure of 50â bar, thereby resulting in the formation of MgNH and molten [LiNH2 -2 LiBH4 ]. That is different from the dehydrogenation pathway of 2 Mg(NH2 )2 -3 LiH sample without LiBH4 , which formed Li2 Mg2 N3 H3 and LiNH2 , as reported previously. In addition, the results of DSC analyses showed that the doped samples exhibited two independent endothermic events, which might be related to two different desorption pathways.
ABSTRACT
The doping effect of Sr(OH)2 on the Mg(NH2)2-2LiH system is investigated considering different amounts of added Sr(OH)2 in the range of 0.05 to 0.2 mol. Experimental results show that both the thermodynamic and the kinetic properties of Mg(NH2)2-2LiH are influenced by the presence of Sr(OH)2. The addition of 0.1 mol Sr(OH)2 leads to a decrease in both the dehydrogenation onset and peak temperatures of ca. 70 and 13 °C, respectively, and an acceleration in the de/re-hydrogenation rates of one time at 150 °C compared to Mg(NH2)2-2LiH alone. Based on differential scanning calorimetry (DSC) analysis, the overall reaction enthalpy of the 0.1 Sr(OH)2-doped sample is calculated to be 44 kJ per mol-H2 and there are two absorption events occurring in the doped sample instead of one in the pristine sample. For the applied experimental conditions, according to the in situ synchrotron radiation powder X-ray diffraction (SR-PXD) and Fourier Transform Infrared spectroscopy (FT-IR) analysis, the reaction mechanism has been finally defined: Sr(OH)2, Mg(NH2)2 and LiH react with each other to form SrO, MgO and LiNH2 during ball milling. After heating, SrO interacts with Mg(NH2)2 producing MgO and Sr(NH2)2. Then Mg(NH2)2, LiNH2 and Sr(NH2)2 react with LiH to produce Li2NH, SrNH, Li2Mg(NH)2 and Li2Mg2(NH)3 in traces. After re-hydrogenation, LiSrH3, LiH and LiNH2 are formed along with amorphous Mg(NH2)2. The reasons for the improved kinetics are: (a) during dehydrogenation, the in situ formation of SrNH appears to increase the interfacial contacts between Mg(NH2)2 and LiH and also weakens the N-H bond of Mg(NH2)2; (b) during absorption, the formation of LiSrH3 at around 150 °C could be the key factor for improving the hydrogenation properties.