scholarly journals Hydrogen Desorption Properties of LiBH4/xLiAlH4 (x = 0.5, 1, 2) Composites

Molecules ◽  
2019 ◽  
Vol 24 (10) ◽  
pp. 1861 ◽  
Author(s):  
Qing He ◽  
Dongdong Zhu ◽  
Xiaocheng Wu ◽  
Duo Dong ◽  
Meng Xu ◽  
...  

A detailed analysis of the dehydrogenation mechanism of LiBH4/xLiAlH4 (x = 0.5, 1, 2) composites was performed by thermogravimetry (TG), differential scanning calorimetry (DSC), mass spectral analysis (MS), powder X-ray diffraction (XRD) and scanning electronic microscopy (SEM), along with kinetic investigations using a Sievert-type apparatus. The results show that the dehydrogenation pathway of LiBH4/xLiAlH4 had a four-step character. The experimental dehydrogenation amount did not reach the theoretical expectations, because the products such as AlB2 and LiAl formed a passivation layer on the surface of Al and the dehydrogenation reactions associated with Al could not be sufficiently carried out. Kinetic investigations discovered a nonlinear relationship between the activation energy (Ea) of dehydrogenation reactions associated with Al and the ratio x, indicating that the Ea was determined both by the concentration of Al produced by the decomposition of LiAlH4 and the amount of free surface of it. Therefore, the amount of effective contact surface of Al is the rate-determining factor for the overall dehydrogenation of the LiBH4/xLiAlH4 composites.

Metals ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 559 ◽  
Author(s):  
Qing He ◽  
Dongdong Zhu ◽  
Xiaocheng Wu ◽  
Duo Dong ◽  
Xiaoying Jiang ◽  
...  

A detailed analysis of the dehydrogenation mechanism and reversibility of LiBH4 doped by as-derived Al (denoted Al*) from AlH3 was performed by thermogravimetry (TG), differential scanning calorimetry (DSC), mass spectral analysis (MS), powder X-ray diffraction (XRD), scanning electronic microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The results show that the dehydrogenation of LiBH4/Al* is a five-step reaction: (1) LiBH4 + Al → LiH + AlB2 + “Li-Al-B-H” + B2H6 + H2; (2) the decomposition of “Li-Al-B-H” compounds liberating H2; (3) 2LiBH4 + Al → 2LiH + AlB2 + 3H2; (4) LiBH4 → LiH + B + 3/2H2; and (5) LiH + Al → LiAl + 1/2H2. Furthermore, the reversibility of the LiBH4/Al* composite is based on the following reaction: LiH + LiAl + AlB2 + 7/2H2 ↔ 2LiBH4 + 2Al. The extent of the dehydrogenation reaction between LiBH4 and Al* greatly depends on the precipitation and growth of reaction products (LiH, AlB2, and LiAl) on the surface of Al*. A passivation shell formed by these products on the Al* is the kinetic barrier to the dehydrogenation of the LiBH4/Al* composite.


Author(s):  
Qing He ◽  
Dongdong Zhu ◽  
Xiaocheng Wu ◽  
Duo Dong ◽  
Xiaoying Jiang ◽  
...  

A detailed analysis of the dehydrogenation mechanism and reversibility of LiBH4 doped by active Al* derived from AlH3 was performed by thermogravimetry (TG), differential scanning calorimetry (DSC), mass spectral analysis (MS), powder X-ray diffraction (XRD), scanning electronic microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results show that the dehydrogenation of LiBH4/Al* is a five-step reaction: (1) LiBH4 + Al → LiH + AlB2 + “Li-Al-B-H” + B2H6 + H2; (2) the decomposition of "Li-Al-B-H" compounds liberating H2; (3) 2LiBH4 + Al → 2LiH + AlB2 + 3H2; (4) LiBH4 → LiH + B + 3/2H2; (5) LiH + Al → LiAl + 1/2H2. And the reversibility of LiBH4/Al* composite is based on equation as follows: LiH + LiAl + AlB2 + 7/2H2 ↔ 2LiBH4 + 2Al. The extent of dehydrogenation reaction between LiBH4 and Al* greatly depends on the precipitation and growth of reaction products (LiH, AlB2 and LiAl, etc.) on the surface of Al*. A passivation shell of Al* formed by these products is the kinetic barrier to the dehydrogenation of LiBH4/Al* composite.


2014 ◽  
Vol 32 (3) ◽  
pp. 385-390
Author(s):  
Aysel Kantürk Figen ◽  
Bilge Coşkuner ◽  
Sabriye Pişkin

AbstractIn the present study, hydrogen desorption properties of magnesium hydride (MgH2) synthesized from modified waste magnesium chips (WMC) were investigated. MgH2 was synthesized by hydrogenation of modified waste magnesium at 320 °C for 90 min under a pressure of 6 × 106 Pa. The modified waste magnesium was prepared by mixing waste magnesium with tetrahydrofuran (THF) and NaCl additions, applying mechanical milling. Next, it was investigated by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) techniques in order to characterize its structural properties. Hydrogen desorption properties were determined by differential scanning calorimetry (DSC) under nitrogen atmosphere at different heating rates (5, 10, and 15 °C/min). Doyle and Kissenger non-isothermal kinetic models were applied to calculate energy (Ea) values, which were found equal to 254.68 kJ/mol and 255.88 kJ/mol, respectively.


2007 ◽  
Vol 128 ◽  
pp. 47-52 ◽  
Author(s):  
R.A. Varin ◽  
Ch. Chiu ◽  
Zbigniew S. Wronski ◽  
Andrzej Calka

In this work oxidized and oxide-free amorphous boron (a-B) powder and elemental Mg were used in an attempt to directly synthesize the Mg(BH4)2 complex hydride by controlled reactive mechanical alloying (CRMA) under hydrogen in a magneto-mill up to 200h. The particle size was refined to the 100-200nm range. Nanocrystalline MgH2 (~6nm crystallite size) was formed within the particles when an oxidized a-B is used. In contrast, a mixture of MgB2 and an amorphous hydride MgHx was formed when an oxide-free a-B was used. Differential scanning calorimetry (DSC) test up to 500°C produced a single endothermic heat event at 357.7°C due to hydrogen desorption. In addition, desorption conducted in a Sieverts-type apparatus revealed ~1.4wt.% of hydrogen release. The X-ray diffraction pattern after DSC test of the 200h milled sample made with oxide-free boron showed the presence of MgB2.


2003 ◽  
Vol 801 ◽  
Author(s):  
A. Bassetti ◽  
E. Bonetti ◽  
A. L. Fiorini ◽  
J. Grbovic ◽  
A. Montone ◽  
...  

ABSTRACTMagnesium carbon nanocomposites for hydrogen storage have been synthesized by ball milling with different amount of benzene, acting as a lubricant. Their microstructure has been studied by X-ray diffraction and scanning electron microscopy, while the hydrogen desorption temperature has been tested by differential scanning calorimetry. Experimental results show that the microstructure after milling, the hydrogenation capabilities of the material and the reactivity with the air are related to the amount of additives. In particular the carbon to benzene ratio seems to play a major role. In fact, with an optimum value of carbon to benzene weight ratio of 1/6, the amount of carbon being 15 wt% of the milled mixture, a decomposition heat equal to 57% of pure MgH2 was measured, even after air manipulation of the sample.


2009 ◽  
Vol 24 (8) ◽  
pp. 2720-2727 ◽  
Author(s):  
Xuebin Yu ◽  
Guanglin Xia ◽  
Zaiping Guo ◽  
Huakun Liu

LiBH4/Al mixtures with various mol ratios were prepared by ball milling. The hydrogen storage properties of the mixtures were evaluated by differential scanning calorimetry/thermogravimetry analyses coupled with mass spectrometry measurements. The phase compositions and chemical state of elements for the LiBH4/Al mixtures before and after hydrogen desorption and absorption reactions were assessed via powder x-ray diffraction, infrared spectroscopy, and x-ray photoelectron spectroscopy. Dehydrogenation results revealed that LiBH4 could react with Al to form AlB2 and AlLi compounds with a two-step decomposition, resulting in improved dehydrogenation. The rehydrogenation experiments were investigated at 600 °C with various H2 pressure. It was found that intermediate hydride was formed firstly at a low H2 pressure of 30 atm, while LiBH4 could be reformed completely after increasing the pressure to 100 atm. Absorption/desorption cycle results showed that the dehydrogenation temperature increased and the hydrogen capacity degraded with the increase of cycle numbers.


Energies ◽  
2020 ◽  
Vol 13 (18) ◽  
pp. 4828
Author(s):  
Isabel Llamas Jansa ◽  
Oliver Friedrichs ◽  
Maximilian Fichtner ◽  
Elisa Gil Bardají ◽  
Andreas Züttel ◽  
...  

The changes introduced by both ball milling and the addition of small amounts of TiF3 in the kinetics of the hydrogen desorption of three different Ca(BH4)2 polymorphs (α, β and γ) have been systematically investigated. The samples with different polymorphic contents, before and after the addition of TiF3, were characterized by powder X-ray diffraction and vibrational spectroscopy. The hydrogen desorption reaction pathways were monitored by differential scanning calorimetry. The hydrogen desorption of Ca(BH4)2 depends strongly on the amount of coexistent α, β and γ polymorphs as well as additional ball milling and added TiF3 to the sample. The addition of TiF3 increased the hydrogen desorption rate without significant dissociation of the fluoride. The combination of an α-Ca(BH4)2 rich sample with 10 mol% of TiF3 and 8 h of milling led to up to 27 °C decrease of the hydrogen desorption peak temperature.


Energies ◽  
2020 ◽  
Vol 13 (8) ◽  
pp. 2080 ◽  
Author(s):  
Magda Pęska ◽  
Tomasz Czujko ◽  
Marek Polański

The Mg-Li binary system is characterized by the presence of α-Mg(Li) and β-Li(Mg) phases, where magnesium exists in ordered and disordered forms that may affect the hydrogenation properties of magnesium. Therefore, the hydrogenation properties of an AZ31 alloy modified by the addition of 4.0 wt.%, 7.5 wt.% and 15.0 wt.% lithium were studied. The morphology (scanning electron microscopy (SEM)), structure, phase composition (X-ray diffraction (XRD)) and hydrogenation properties (differential scanning calorimetry (DSC)) of AZ31 with various lithium contents were investigated. It was found that the susceptibility of magnesium in the form of α-Mg(Li) to hydrogenation was higher than that for the magnesium occupying a disordered position in β-Li(Mg) solid solutions. Magnesium hydride was obtained as a result of hydrogenation of the AZ31 alloy that was modified with 4.0 wt.%, 7.5 wt.% and 15.0 wt.% additions of lithium, and was characterized by high hydrogen desorption activation energies of 250, 187 and 224 kJ/mol, respectively.


Molecules ◽  
2021 ◽  
Vol 26 (16) ◽  
pp. 4853
Author(s):  
Mohammad R. Ghaani ◽  
Michele Catti ◽  
Niall J. English

Adding a secondary complex metal hydride can either kinetically or thermodynamically facilitate dehydrogenation reactions. Adding Mg2FeH6 to LiBH4 is energetically favoured, since FeB and MgB2 are formed as stable intermediate compounds during dehydrogenation reactions. Such “hydride destabilisation” enhances H2-release thermodynamics from H2-storage materials. Samples of the LiBH4 and Mg2FeH6 with a 2:1 molar ratio were mixed and decomposed under three different conditions (dynamic decomposition under vacuum, dynamic decomposition under a hydrogen atmosphere, and isothermal decomposition). In situ synchrotron X-ray diffraction results revealed the influence of decomposition conditions on the selected reaction path. Dynamic decomposition of Mg2FeH6–LiBH4 under vacuum, or isothermal decomposition at low temperatures, was found to induce pure decomposition of LiBH4, whilst mixed decomposition of LiBH4 + Mg and formation of MgB2 were achieved via high-temperature isothermal dehydrogenation.


Author(s):  
D. Nagasamy Venkatesh ◽  
S. Karthick ◽  
M. Umesh ◽  
G. Vivek ◽  
R.M. Valliappan ◽  
...  

Roxythromycin/ β-cyclodextrin (Roxy/ β-CD) dispersions were prepared with a view to study the influence of β-CD on the solubility and dissolution rate of this poorly soluble drug. Phase-solubility profile indicated that the solubility of roxythromycin was significantly increased in the presence of β-cyclodextrin and was classified as AL-type, indicating the 1:1 stoichiometric inclusion complexes. Physical characterization of the prepared systems was carried out by differential scanning calorimetry (DSC), X-ray diffraction studies (XRD) and IR studies. Solid state characterization of the drug β-CD binary system using XRD, FTIR and DSC revealed distinct loss of drug crystallinity in the formulation, ostensibly accounting for enhancement of dissolution rate.


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