Functions of MgH(2) in hydrogen storage reactions of the 6LiBH(4)-CaH(2) reactive hydride composite

A significant improvement of hydrogen storage properties was achieved by introducing MgH(2) into the 6LiBH(4)-CaH(2) system. It was found that ～8.0 wt% of hydrogen could be reversibly stored in a 6LiBH(4)-CaH(2)-3MgH(2) composite below 400 °C and 100 bar of hydrogen pressure with a stepwise reaction, which is superior to the pristine 6LiBH(4)-CaH(2) and LiBH(4) samples. Upon dehydriding, MgH(2) first decomposed to convert to Mg and liberate hydrogen with an on-set temperature of ～290 °C. Subsequently, LiBH(4) reacted with CaH(2) to form CaB(6) and LiH in addition to further hydrogen release. Hydrogen desorption from the 6LiBH(4)-CaH(2)-3MgH(2) composite finished at ～430 °C in non-isothermal model, a 160 °C reduction relative to the 6LiBH(4)-CaH(2) sample. JMA analyses revealed that hydrogen desorption was a diffusion-controlled reaction rather than an interface reaction-controlled process. The newly produced Mg of the first-step dehydrogenation possibly acts as the heterogeneous nucleation center of the resultant products of the second-step dehydrogenation, which diminishes the energy barrier and facilitates nucleation and growth, consequently reducing the operating temperature and improving the kinetics of hydrogen storage.     

A new ammine dual-cation (Li, Mg) borohydride: synthesis, structure, and dehydrogenation enhancement

A new ammine dual-cation borohydride, LiMg(BH(4))(3)(NH(3))(2), has been successfully synthesized simply by ball-milling of Mg(BH(4))(2) and LiBH(4)·NH(3). Structure analysis of the synthesized LiMg(BH(4))(3)(NH(3))(2) revealed that it crystallized in the space group P6(3) (no. 173) with lattice parameters of a=b=8.0002(1) ?, c=8.4276(1) ?, α=β=90°, and γ=120° at 50 °C. A three-dimensional architecture is built up through corner-connecting BH(4) units. Strong N-H···H-B dihydrogen bonds exist between the NH(3) and BH(4) units, enabling LiMg(BH(4))(3)(NH(3))(2) to undergo dehydrogenation at a much lower temperature. Dehydrogenation studies have revealed that the LiMg(BH(4))(3)(NH(3))(2)/LiBH(4) composite is able to release over 8 wt% hydrogen below 200 °C, which is comparable to that released by Mg(BH(4))(3)(NH(3))(2). More importantly, it was found that release of the byproduct NH(3) in this system can be completely suppressed by adjusting the ratio of Mg(BH(4))(2) and LiBH(4)·NH(3). This chemical control route highlights a potential method for modifying the dehydrogenation properties of other ammine borohydride systems.     

Stability and reversibility of LiBH4

LiBH4 is a complex hydride and exhibits a high gravimetric hydrogen density of 18.5 wt %. Therefore it is a promising hydrogen storage material for mobile applications. The stability of LiBH4 was investigated by pcT (pressure, concentration, and temperature) measurements under constant hydrogen flows and extrapolated to equilibrium. According to the van 't Hoff equation the following thermodynamic parameters are determined for the desorption: enthalpy of reaction DeltarH = 74 kJ mol-1 H2 and entropy of reaction DeltarS = 115 J K-1 mol-1 H2. LiBH4 decomposes to LiH + B + 3/2H2 and can theoretically release 13.9 wt % hydrogen for this reaction. It is shown that the reaction can be reversed at a temperature of 600 degrees C and at a pressure of 155 bar. The formation of LiBH4 was confirmed by XRD (X-ray diffraction). In the rehydrided material 8.3 wt % hydrogen was desorbed in a TPD (temperature-programmed desorption) measurement compared to 10.9 wt % desorbed in the first dehydrogenation.     

3LiBH4/CeF3体系的放氢性能及机制

采用球磨法制备了3LiBH₄/CeF₃反应体系, 通过压力-组成-温度(PCT)测试仪、 X射线衍射仪(XRD)和傅里叶变换红外光谱仪(FTIR)研究了体系的放氢性能、 反应机制及性能改善机理. 结果表明, 3LiBH₄/CeF₃体系在295 ℃左右快速放氢, 总放氢量为4.1%(质量分数). 放氢过程中CeF₃与LiBH₄直接发生反应: 3LiBH₄+CeF₃1/2CeB₆+1/2CeH₂+3LiF+11/2H₂. 与纯LiBH₄相比, 放氢热力学稳定性和表观活化能的降低是3LiBH₄/CeF₃体系放氢温度下降的主要原因.     

Monoammoniate of calcium amidoborane: synthesis, structure, and hydrogen-storage properties

The monoammoniate of calcium amidoborane, Ca(NH(2)BH(3))(2)·NH(3), was synthesized by ball milling an equimolar mixture of CaNH and AB. Its crystal structure has been determined and was found to contain a dihydrogen-bonded network. Thermal decomposition under an open-system begins with the evolution of about 1 equivalent/formula unit (equiv.) of NH(3) at temperatures <100 °C followed by the decomposition of Ca(NH(2)BH(3))(2) to release hydrogen. In a closed-system thermal decomposition process, hydrogen is liberated in two stages, at about 70 and 180 °C, with the first stage corresponding to an exothermic process. It has been found that the presence of the coordinated NH(3) has induced the dehydrogenation to occur at low temperature. At the end of the dehydrogenation, about 6 equiv. (～ 10.2 wt %) of hydrogen can be released, giving rise to the formation of CaB(2)N(3)H.     

Dehydrogenation tuning of ammine borohydrides using double-metal cations

The strategy of using double-cations to tune the temperature and purity of dehydrogenation of ammine borohydrides is reported. The first double-cation ammine borohydride, Li(2)Al(BH(4))(5)·6NH(3), which forms a novel structure with ordered arrangement of Al(NH(3))(6)(3+) ammine complexes and Li(2)(BH(4))(5)(3-) complex anions, is found to release over 10.0 wt % hydrogen below 120 °C with favorable kinetics and high H-purity (>99%).     

Reversible storage of hydrogen in destabilized LiBH4

Destabilization of LiBH4 for reversible hydrogen storage has been studied using MgH2 as a destabilizing additive. Mechanically milled mixtures of LiBH4 + (1/2)MgH2 or LiH + (1/2)MgB2 including 2-3 mol % TiCl3 are shown to reversibly store 8-10 wt % hydrogen. Variation of the equilibrium pressure obtained from isotherms measured at 315-400 degrees C indicate that addition of MgH2 lowers the hydrogenation/dehydrogenation enthalpy by 25 kJ/(mol of H2) compared with pure LiBH4. Formation of MgB2 upon dehydrogenation stabilizes the dehydrogenated state and, thereby, destabilizes the LiBH4. Extrapolation of the isotherm data yields a predicted equilibrium pressure of 1 bar at approximately 225 degrees C. However, the kinetics were too slow for direct measurements at these temperatures.     

化学计量比和放氢背压对LiBH4+xMg2NiH4体系放氢性能的影响

研究了不同化学计量比(x=0.25, 0.5, 0.75, 1.0, 1.25)和放氢背压(1×10-4和0.4 MPa)对LiBH4+xMg2NiH4复合体系吸放氢性能的影响. 结果表明, 随着化学计量比(x)的增加, 复合体系的放氢温度逐渐降低, 放氢动力学性能得到提高, 但放氢容量逐渐降低; 其中, 在1×10-4和0.4 MPa初始放氢背压下, LiBH4+0.75Mg2NiH4体系具有最佳放氢动力学性能和较高的储氢容量. 结果表明, 放氢背压和化学计量比均会对高温下液相LiBH4 与固态Mg2NiH4 的润湿性产生影响, 进而影响复合体系的放氢路径和放氢动力学性能.     

Solid-state NMR study of Li-assisted dehydrogenation of ammonia borane

The mechanism of thermochemical dehydrogenation of the 1:3 mixture of Li(3)AlH(6) and NH(3)BH(3) (AB) has been studied by the extensive use of solid-state NMR spectroscopy and theoretical calculations. The activation energy for the dehydrogenation is estimated to be 110 kJ mol(-1), which is lower than for pristine AB (184 kJ mol(-1)). The major hydrogen release from the mixture occurs at 60 and 72 °C, which compares favorably with pristine AB and related hydrogen storage materials, such as lithium amidoborane (LiNH(2)BH(3), LiAB). The NMR studies suggest that Li(3)AlH(6) improves the dehydrogenation kinetics of AB by forming an intermediate compound (LiAB)(x)(AB)(1-x). A part of AB in the mixture transforms into LiAB to form this intermediate, which accelerates the subsequent formation of branched polyaminoborane species and further release of hydrogen. The detailed reaction mechanism, in particular the role of lithium, revealed in the present study highlights new opportunities for using ammonia borane and its derivatives as hydrogen storage materials.     

Ammonium octahydrotriborate (NH4B3H8): new synthesis, structure, and hydrolytic hydrogen release

A metathesis reaction between unsolvated NaB(3)H(8) and NH(4)Cl provides a simple and high-yield synthesis of NH(4)B(3)H(8). Structure determination through X-ray single crystal diffraction analysis reveals weak N-H(δ+)---H(δ-)-B interaction in NH(4)B(3)H(8) and strong N-H(δ+)---H(δ-)-B interaction in NH(4)B(3)H(8)·18-crown-6·THF adduct. Pyrolysis of NH(4)B(3)H(8) leads to the formation of hydrogen gas with appreciable amounts of other volatile boranes below 160 °C. Hydrolysis experiments show that upon addition of catalysts, NH(4)B(3)H(8) releases up to 7.5 materials wt % hydrogen.     

Promotion of hydrogen release from ammonia borane with magnesium nitride

Hydrogen release from ammonia borane (NH(3)BH(3), AB) can be greatly promoted by mechanical milling with magnesium nitride (Mg(3)N(2)). For example, a post-milled 6AB/Mg(3)N(2) sample started to release hydrogen from ～65 °C and gave a material-based hydrogen capacity of ～11 wt% upon heating to 300 °C. In addition to the improved dehydrogenation kinetics, the 6AB/Mg(3)N(2) sample also showed satisfactory performance in suppressing the volatile byproducts. X-ray diffraction, Fourier transform infrared spectroscopy and solid-state (11)B MAS NMR, as well as a series of designed experiments, were carried out to gain mechanistic understanding of the property improvements that arise from addition of Mg(3)N(2). Our study found that the formation of 3Mg(NH(2)BH(3))(2)·2NH(3), which is in single or mixed amidoborane ammoniate phases in nature, is an important mechanistic step in the dehydrogenation process of the 6AB/Mg(3)N(2) sample.     

Nanoconfinement of lithium borohydride in Cu-MOFs towards low temperature dehydrogenation

Successful synthesis and investigation of a new material that uses copper-metal-organic frameworks (Cu-MOFs) as the template for loading LiBH(4) are reported. The nanoconfinement of LiBH(4) in the pores of Cu-MOFs results in an interaction between LiBH(4) and Cu(2+) ions, enabling the LiBH(4)@Cu-MOFs system to achieve a much lower dehydrogenation temperature than pristine LiBH(4).     

Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4: Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra

The dehydrogenation enthalpies of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski's direct method. The dehydrogenation of Ca(AlH(4))(2) is exothermic, indicating a metastable hydride. Calculations for CaAlH(5) including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH(4) with CaH(2) is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH(4))(2) and CaAlH(5) calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH(5) is presented in the more useful standard setting of P2(1)c symmetry and the phonon density of states of CaAlH(5), significantly different to other common complex metal hydrides, is rationalized.     

Cobalt-catalyzed hydrogen desorption from the LiNH2-LiBH4 system

A doping of 5 wt% CoCl2 considerably decreases the dehydrogenation temperature of a mixture of LiNH2 and LiBH4. More that 8 wt% of hydrogen can be released at ca. 155 degrees C. X-Ray absorption near edge structure (XANES) spectroscopy indicated the formation of metallic Co after ball milling CoCl2 with LiNH2 and LiBH4. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements revealed that Co particles have poor crystallinity and are finely dispersed in the sample, which could lead to a high catalytic efficiency.     

Pressure-enhanced dehydrogenation reaction of the LiBH4-YH3 composite

The increase in hydrogen back pressure unexpectedly enhances the overall dehydrogenation reaction rate of the 4LiBH(4) + YH(3) composite significantly. Also, argon back pressure has a similar influence on the composite. Gas back pressure seems to enhance the dehydrogenation reaction by kinetically suppressing the formation of the diborane by-product.     

In Situ Synthesis of 3D Flower‐Like Nanocrystalline Ni/C and its Effect on Hydrogen Storage Properties of LiAlH4

Lithium alanate (LiAlH₄) is of particular interest as one of the most promising candidates for solid‐state hydrogen storage. Unfortunately, high dehydrogenation temperatures and relatively slow kinetics limit its practical applications. Herein, 3D flower‐like nanocrystalline Ni/C, composed of highly dispersed Ni nanoparticles and interlaced carbon flakes, was synthesized in situ. The as‐synthesized nanocrystalline Ni/C significantly decreased the dehydrogenation temperature and dramatically improved the dehydrogenation kinetics of LiAlH₄. It was found that the LiAlH₄ sample with 10 wt % Ni/C (LiAlH₄‐10 wt %Ni/C) began hydrogen desorption at approximately 48 °C, which is very close to ambient temperature. Approximately 6.3 wt % H₂ was released from LiAlH₄‐10 wt %Ni/C within 60 min at 140 °C, whereas pristine LiAlH₄ only released 0.52 wt % H₂ under identical conditions. More importantly, the dehydrogenated products can partially rehydrogenate at 300 °C under 4 MPa H₂. The synergetic effect of the flower‐like carbon substrate and Ni active species contributes to the significantly reduced dehydrogenation temperatures and improved kinetics.     

Correlation between composition and hydrogen storage behaviors of the Li2NH-MgNH combination system

Hydrogen storage performances of a Li(2)NH-xMgNH combination system (x = 0, 0.5, 1 and 2) are investigated for the first time. It is found that the hydrogenated samples with MgNH exhibit a significant reduction in the dehydrogenation temperatures. Mechanistic investigations reveal that there is a strong dependence of the hydrogen storage reaction process on the molar ratio between MgNH and Li(2)NH. As a consequence, tuning of thermodynamics is achieved for hydrogen storage in the Li(2)NH-xMgNH system by changing the reaction routes, which is ascertained to be the primary reason for the reduction in the operating temperature for hydrogen desorption. Specifically, it is found that under 105 atm hydrogen (140-280 °C) 5.6 wt% hydrogen is reversibly stored in the Li(2)NH-0.5MgNH combination system, which is greater than in the well-investigated Mg(NH(2))(2)-2LiH system.     

LiBH4-X（X=O,F和Cl）体系解氢性能的第一原理计算

采用基于密度泛函理论的第一原理方法,计算了LiBH4-X(X=O,F和Cl)体系的晶体与电子结构及解氢性能.生成热和H原子解离能的计算结果表明:O原子掺杂优先占据LiBH4间隙位,F置换氢原子位,而Cl则取代BH4单元;O,F和Cl掺杂的LiBH4体系结构稳定性发生变化,其中O提高体系解氢效果明显,而F和Cl掺杂受H原子区域环境的影响.态密度、Mulliken电子占据数和电子密度的分析结果表明:B—H之间较强的共价键是LiBH4结构稳定、解氢困难的电子结构根源,O,F和Cl对LiBH4解氢能力影响主要是掺杂改变了H的s态与B的sp态的杂化特性、以及BH4单元与Li的成键作用.     

Silica hollow nanospheres as new nanoscaffold materials to enhance hydrogen releasing from ammonia borane

Silica hollow nanospheres (SHNS) are used as new nanoscaffold materials to confine ammonia borane (NH(3)BH(3), AB) for enhancing the dehydrogenation process. Different loading levels of AB in SHNS are considered and AB/4SHNS (with AB content of approximately 20 wt%) shows the best result. The onset temperature of the dehydrogenation of AB in SHNS is as low as 70 °C with the peak temperature at 99 °C and no other gases such as borazine and ammonia are detected. Furthermore, within 60 min at 85 °C, 0.53 equivalent of hydrogen is released and the activation energy is 97.6 kJ mol(-1). Through FT-IR, Raman spectrum and density functional theory (DFT) calculation, it is found that nanoconfinement effect combined with SiO-HH-B interaction is essential for the enhancement of hydrogen releasing.