The effects of ball milling and nanometric nickel additive on the hydrogen desorption from lithium borohydride and manganese chloride (3LiBH4+MnCl2) mixture

Varin, R.A.; Zbroniec, L.

doi:10.1016/j.ijhydene.2010.01.137

Cited by 35 publications

(51 citation statements)

References 11 publications

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“…Similar ion-exchange be the most signiÞcant element among all of IVB group in interactions (4) could take place in case of LiBH4 with MgCl2 Periodic Table. In conclusion of the discussion, it would be [17], MnCl2 [18] or ZnF2 [19], and as in the present paper, with reasonable to proceed the studying about the effects of tita-TiF4. In case of RHCs, based on lithium borohydride, the nium additives on hydrogen sorption of LiHeMgB2 composite additives likely react with LiBH4 in similar way.…”

Section: Atr-ir Spectroscopy Of Milled and Hydrogenated Lihemgb 2 Ex mentioning

confidence: 68%

Enhanced hydrogen uptake/release in 2LiH–MgB 2 composite with titanium additives

Saldan

Campesi

Zavorotynska

et al. 2012

International Journal of Hydrogen Energy

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The influence of different titanium additives on hydrogen sorption in LiHeMgB 2 system has been investigated. For all the composites LiHeMgB 2 eX (X ¼ TiF 4 , TiO 2 , TiN, and TiC), prepared by ball-milling in molar ratios 2:1:0.1, Þve hydrogen uptake/release cycles were performed. In-situ synchrotron radiation powder X-ray diffraction (SR-PXD) and attenu-ated total reßection infrared spectroscopy (ATR-IR) have been used to characterize crystal phases developed during the hydrogen absorptionedesorption cycles.All the composites with the titanium additives displayed an improvement of reaction kinetics, especially during hydrogen desorption. The LiHeMgB 2 eTiO 2 system reached a storage of about 7.6 wt % H 2 in w1.8 h for absorption and w2.7 h for desorption. Using in-situ SR-PXD measurements, magnesium was detected as an intermediate phase during hydrogen desorption for all composites. In the composite with TiF 4 addition the formation of new phases (TiB 2 and LiF) were observed. Characteristic diffraction peaks of TiO 2 , TiN and TiC additives were always present during hydrogen absorptionedesorption. For all as-milled composites, ATR-IR spectra did not show any signals for borohydrides, while for all hydrogenated composites BeH stretching (2450e2150 cm 1 ) and BeH bending (1350e1000 cm 1 ) bands were exactly the same as for commercial LiBH 4 . IntroductionHydrogen can be one of the alternative energy carriers, which should replace the traditional fossil fuels in the near future. One of the promising materials for hydrogen mobile applica-tion which has been studied approximately for 10 years is LiBH 4 [1]. Having high gravimetric and volumetric hydrogen density, this material, though, exhibits unfavorable kinetics and thermodynamics for real application in fuel cells. Recently, it was found that LiBH 4 can be destabilized by the addition of MgH 2 , showing better decomposition kinetics with respect to the pure compound [2]. A detailed analysis of the reversible interaction between LiBH 4 and MgH 2 was made in [3] and can be summarized as follow: 2LiBH 4 þ MgH 2 4 2LiBH 4 þ Mg þ H 2 4 2LiH þ MgB 2 þ 4H 2 (1)The direct reactions (1) take place at w400 C. Opposite reactions, with simultaneous formation of LiBH 4 and MgH 2 under 50 bar of H 2 , was conÞrmed at the temperatures 250e300 C [3]. It was observed that suitable additives might decrease reaction temperatures and improve kinetics of Eq. (1). Experimental evidence of kinetic improvement for reversible middle-temperature Na, Li and Al based complex hydrides doped by titanium additives appeared in 1997 [4]. It has also been reported that the kinetic improvement of the reaction (1) was reached by addition of 1 mol% of TiF 3 [5]. The property enhancement arising upon this additive persists well in the subsequent hydrogen uptake/release cycles. Another prom-inent example of the additives effect was the composite LiBH 4 eMgH 2 eTi{OCH(CH 3 ) 2 } 4 mixed in molar ratio 2:1:0.1 [6]. After ball-milling TiO 2 anatase was found and during 1-st hydrogen desorptio...

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Section: Atr-ir Spectroscopy Of Milled and Hydrogenated Lihemgb 2 Ex mentioning

confidence: 68%

Enhanced hydrogen uptake/release in 2LiH–MgB 2 composite with titanium additives

Saldan

Campesi

Zavorotynska

et al. 2012

International Journal of Hydrogen Energy

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“…[94]. In addition, there are several other M(BH 4 ) n (e.g., M = Zn, Al, Ti, Mn and Zr) [95][96][97][98][99][100][101][102][103]. Most of these were found to be irreversible due to their low melting temperatures and the release of diborane with hydrogen.…”

Section: Fundamentals Of Hydrogen Storage Propertiesmentioning

confidence: 99%

Recent Progress in Metal Borohydrides for Hydrogen Storage

et al. 2011

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Abstract:The prerequisite for widespread use of hydrogen as an energy carrier is the development of new materials that can safely store it at high gravimetric and volumetric densities. Metal borohydrides M(BH 4 ) n (n is the valence of metal M), in particular, have high hydrogen density, and are therefore regarded as one such potential hydrogen storage material. For fuel cell vehicles, the goal for on-board storage systems is to achieve reversible store at high density but moderate temperature and hydrogen pressure. To this end, a large amount of effort has been devoted to improvements in their thermodynamic and kinetic aspects. This review provides an overview of recent research activity on various M(BH 4 ) n , with a focus on the fundamental dehydrogenation and rehydrogenation properties and on providing guidance for material design in terms of tailoring thermodynamics and promoting kinetics for hydrogen storage.

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“…The hydride powder mixtures with the ball-to-powder weight ratio R = 132 were subsequently processed by controlled ball milling for selected time durations in the magneto-mill Uni-Ball-Mill 5 under IMP68 mode. This is a high impact energy mode with two very strong Nd-Fe-B magnets at the 6 and 8 o'clock positions and 4 steel balls (each 25 mm in diameter) in the vial [2,[11][12][13][14][15]. The pressure of high purity hydrogen (purity 99.999%: O 2 < 2 ppm; H 2 O < 3 ppm; CO 2 < 1 ppm; N 2 < 6 ppm; CO < 1 ppm; THC < 1 ppm) in the vial was kept constant at ~600 kPa during the entire milling process.…”

Section: Experimental Methodsmentioning

confidence: 99%

Mechanical and Thermal Dehydrogenation of Lithium Alanate (LiAlH4) and Lithium Amide (LiNH2) Hydride Composites

Varin

Zbroniec

2012

Crystals

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Hydrogen storage properties of the (nLiAlH 4 + LiNH 2 ) hydride composite where n = 1, 3, 11.5 and 30, synthesized by high energy ball milling have been investigated. The composite with the molar ratio n = 1 releases large quantities of H 2 (up to ~5 wt.%) during ball milling up to 100-150 min. The quantity of released H 2 rapidly decreases for the molar ratio n = 3 and is not observed for n = 11.5 and 30. The XRD studies indicate that the H 2 release is a result of a solid state decomposition of LiAlH 4 into (1/3)Li 3 AlH 6 + (2/3)Al + H 2 and subsequently decomposition of (1/3)Li 3 AlH 6 into LiH + (1/3)Al + 0.5H 2 . Apparently, LiAlH 4 is profoundly destabilized during ball milling by the presence of a large quantity of LiNH 2 (37.7 wt.%) in the n = 1 composite. The rate of dehydrogenation at 100-170 °C (at 1 bar H 2 ) is adversely affected by insufficient microstructural refinement, as observed for the n = 1 composite, which was milled for only 2 min to avoid H 2 discharge during milling. XRD studies show that isothermal dehydrogenation of (nLiAlH 4 + LiNH 2 ) occurs by the same LiAlH 4 decomposition reactions as those found during ball milling. The ball milled n = 1 composite stored under Ar at 80 °C slowly discharges large quantities of H 2 approaching 3.5 wt.% after 8 days of storage.

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The effects of ball milling and nanometric nickel additive on the hydrogen desorption from lithium borohydride and manganese chloride (3LiBH4+MnCl2) mixture

Cited by 35 publications

References 11 publications

Enhanced hydrogen uptake/release in 2LiH–MgB 2 composite with titanium additives

Enhanced hydrogen uptake/release in 2LiH–MgB 2 composite with titanium additives

Recent Progress in Metal Borohydrides for Hydrogen Storage

Mechanical and Thermal Dehydrogenation of Lithium Alanate (LiAlH4) and Lithium Amide (LiNH2) Hydride Composites

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