A novel catalytic route for hydrogenation–dehydrogenation of 2LiH + MgB2via in situ formed core–shell LixTiO2nanoparticles

Puszkiel, Julián; Riglos, María Victoria Castro; Ramallo‐López, José M.; Mizrahi, Martín; Karimi, Fahim; Santoru, Antonio; Hoell, Armin; Gennari, F.C.; Larochette, P. Arneodo; Pistidda, Claudio; Klassen, Thomas; Colbe, José M. Bellosta von; Dornheim, Martin

doi:10.1039/c7ta03117c

Cited by 29 publications

(48 citation statements)

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“…Investigations into reaction pathways under different temperatures, hydrogen pressures, and stoichiometric compositions were carried out in order to understand the behavior of the Li-RHC and try to optimize its operative conditions. These investigations were focused mainly on the dehydrogenation pathways [33][34][35][36][37][38][39][40]. In 2007, Bösenberg et al [33] first reported the global hydrogenation and dehydrogenation reaction mechanisms of Li-RHC under dynamic conditions.…”

Section: Destabilized Mgh2-2libh4 System: Li-rhcmentioning

confidence: 99%

“…It was suggested that this stable compound hinders the full reversibility, and thus it is responsible for the loss of hydrogen capacity [56]. Puszkiel et al [39] and Jepsen et al [40] also studied the dehydrogenation behavior of Li-RHC under equilibrium conditions by PCI curve measurements with different additives, i.e., 2LiH + MgB 2 + 5 mol% TiO 2 [39] and 2LiH + MgB 2 + 5 mol% TiCl 3 [40]. The two-step reaction was also verified in both cases, providing enthalpy values in excellent agreement with the ones for MgH 2 for the higher plateau (~76 kJ mol −1 H 2 [39] and~73 kJ mol −1 H 2 [40]), and enthalpy values in the order of 50-60 kJ mol −1 H 2 for the second plateau ascribed to the dehydrogenation of LiBH 4 and formation of MgB 2 + LiH (~61 kJ mol −1 H 2 [39] and~53 kJ mol −1 H 2 [40]).…”

Section: Destabilized Mgh2-2libh4 System: Li-rhcmentioning

confidence: 99%

“…Puszkiel et al [39] and Jepsen et al [40] also studied the dehydrogenation behavior of Li-RHC under equilibrium conditions by PCI curve measurements with different additives, i.e., 2LiH + MgB 2 + 5 mol% TiO 2 [39] and 2LiH + MgB 2 + 5 mol% TiCl 3 [40]. The two-step reaction was also verified in both cases, providing enthalpy values in excellent agreement with the ones for MgH 2 for the higher plateau (~76 kJ mol −1 H 2 [39] and~73 kJ mol −1 H 2 [40]), and enthalpy values in the order of 50-60 kJ mol −1 H 2 for the second plateau ascribed to the dehydrogenation of LiBH 4 and formation of MgB 2 + LiH (~61 kJ mol −1 H 2 [39] and~53 kJ mol −1 H 2 [40]). In the case of the hydrogenation process under equilibrium conditions, Cova et al [56] identified two temperature regions below and above 413 • C. On the one hand, above 413 • C, two plateaus were noticed: the first (lower) one corresponding to the formation of LiBH 4 from MgB 2 and LiH and the second (higher) belonging to the hydrogenation of Mg. Noteworthy, the enthalpy value for the formation of LiBH 4 amounted to~41 kJ mol −1 H 2 , in accordance with the 40.5 kJ mol −1 H 2 reported by Vajo et al [29], while the obtained enthalpy value for the hydrogenation of Mg (higher plateau) was~76 kJ mol −1 H 2 .…”

Section: Destabilized Mgh2-2libh4 System: Li-rhcmentioning

confidence: 99%

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Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches

et al. 2019

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Hydrogen technology has become essential to fulfill our mobile and stationary energy needs in a global low–carbon energy system. The non-renewability of fossil fuels and the increasing environmental problems caused by our fossil fuel–running economy have led to our efforts towards the application of hydrogen as an energy vector. However, the development of volumetric and gravimetric efficient hydrogen storage media is still to be addressed. LiBH4 is one of the most interesting media to store hydrogen as a compound due to its large gravimetric (18.5 wt.%) and volumetric (121 kgH2/m3) hydrogen densities. In this review, we focus on some of the main explored approaches to tune the thermodynamics and kinetics of LiBH4: (I) LiBH4 + MgH2 destabilized system, (II) metal and metal hydride added LiBH4, (III) destabilization of LiBH4 by rare-earth metal hydrides, and (IV) the nanoconfinement of LiBH4 and destabilized LiBH4 hydride systems. Thorough discussions about the reaction pathways, destabilizing and catalytic effects of metals and metal hydrides, novel synthesis processes of rare earth destabilizing agents, and all the essential aspects of nanoconfinement are led.

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Section: Destabilized Mgh2-2libh4 System: Li-rhcmentioning

confidence: 99%

Section: Destabilized Mgh2-2libh4 System: Li-rhcmentioning

confidence: 99%

Section: Destabilized Mgh2-2libh4 System: Li-rhcmentioning

confidence: 99%

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Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches

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“…2LiBH 4 + MgH 2 2LiH + MgB 2 + 4H 2 (52) In the last decade this system has been thoroughly investigated with respect to reaction pathway, temperature and hydrogen pressure boundaries, microstructure, effect of additives on the reaction kinetics, and nanoconfinement [159][160][161][162][163][164][165][166][167][168][169][170][171][172][173].…”

Section: Libhmentioning

confidence: 99%

Tetrahydroborates: Development and Potential as Hydrogen Storage Medium

et al. 2017

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Abstract:The use of fossil fuels as an energy supply becomes increasingly problematic from the point of view of both environmental emissions and energy sustainability. As an alternative, hydrogen is widely regarded as a key element for a potential energy solution. However, differently from fossil fuels such as oil, gas, and coal, the production of hydrogen requires energy. Alternative and intermittent renewable energy sources such as solar power, wind power, etc., present multiple advantages for the production of hydrogen. On the one hand, the renewable sources contribute to a remarkable reduction of pollutants released to the air and on the other hand, they significantly enhance the sustainability of energy supply. In addition, the storage of energy in form of hydrogen has a huge potential to balance an effective and synergetic utilization of renewable energy sources. In this regard, hydrogen storage technology is a key technology towards the practical application of hydrogen as "energy carrier". Among the methods available to store hydrogen, solid-state storage is the most attractive alternative from both the safety and the volumetric energy density points of view. Because of their appealing hydrogen content, complex hydrides and complex hydride-based systems have attracted considerable attention as potential energy vectors for mobile and stationary applications. In this review, the progresses made over the last century on the synthesis and development of tetrahydroborates and tetrahydroborate-based systems for hydrogen storage purposes are summarized.

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“…Therefore, the design/synthesis of new additives is mandatory in order to achieve long-lasting absorption/desorption properties. TiO 2 is one of the low-cost additives which enhance the hydrogen storage properties of the 2LiBH 4 + MgH 2 reactive hydride composite (RHC) system [44][45][46] . Puszkiel et al showed that 2LiH + MgB 2 /2LiBH 4 + MgH 2 RHC system doped with core-shell Li x TiO 2 nanoparticles shows improved the kinetic and cycling behaviour 44 .…”

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Improved kinetic behaviour of Mg(NH2)2-2LiH doped with nanostructured K-modified-LixTiyOz for hydrogen storage

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Puszkiel

Riglos

et al. 2020

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the system Mg(nH 2 ) 2 + 2LiH is considered as an interesting solid-state hydrogen storage material owing to its low thermodynamic stability of ca. 40 kJ/mol H 2 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 Li x ti y o z on the absorption/ desorption behaviour of the Mg(nH 2 ) 2 + 2LiH system. In comparison with the pristine Mg(NH 2 ) 2 + 2LiH, the system containing a tiny amount of nanostructured K-modified Li x ti y o z shows enhanced absorption/ desorption behaviour. The doped material presents a sensibly reduced (∼30 °C) desorption onset temperature, notably shorter hydrogen absorption/desorption times and reversible hydrogen capacity of about 3 wt.% H 2 upon cycling. Studies on the absorption/desorption processes and micro/nanostructural characterizations of the Mg(nH 2 ) 2 + 2LiH + K-modified Li x ti y o z system hint to the fact that the presence of in situ formed nanostructure K 2 tio 3 is the main responsible for the observed improved kinetic behaviour. Scientific RepoRtS |(2020) 10:8 | https://doi.org/10.1038/s41598-019-55770-y www.nature.com/scientificreports www.nature.com/scientificreports/ According to the calculated thermodynamic properties of the Mg(NH 2 ) 2 + 2LiH stoichiometric mixture, operating temperatures of 90 °C can be achieved at 1 bar 18 . However, sufficient dehydrogenation rates, even after intense ball milling treatment, can be obtained only at temperatures above 180 °C due to harsh kinetic constraints 19 . Several attempts have been made in order to improve the sluggish dehydrogenation behaviour of the Mg(NH 2 ) 2 + 2LiH composite system . Potassium containing additives effectively reduce the dehydrogenation peak temperature down to 130 °C, which is ∼50 °C lower than that of pristine Mg(NH 2 ) 2 + 2LiH 40-42 . However, due to segregation phenomena that occurs at high-temperature (≥180 °C) upon cycling, the inhomogeneous distribution of the K-species reduces their catalytic activity 43 . Therefore, the design/synthesis of new additives is mandatory in order to achieve long-lasting absorption/desorption properties. TiO 2 is one of the low-cost additives which enhance the hydrogen storage properties of the 2LiBH 4 + MgH 2 reactive hydride composite (RHC) system [44][45][46] . Puszkiel et al. showed that 2LiH + MgB 2 /2LiBH 4 + MgH 2 RHC system doped with core-shell Li x TiO 2 nanoparticles shows improved the kinetic and cycling behaviour 44 . It was found that the core-shell Li x TiO 2 nanoparticles act as Li + pumps, increasing Li + mobility, hence accounting for the observed enhanced hydrogen storage properties. Studies on reaction mechanism of Mg(NH 2 ) 2 + LiH system showed that diffusion of small ions (e.g., Li + , Mg +2 , and H + ) might account for the improved reaction kinetics [47][48][49][50] . In this work, we investigate the effect of Li x Ti y O z and potassium-modified Li x Ti ...

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A novel catalytic route for hydrogenation–dehydrogenation of 2LiH + MgB₂via in situ formed core–shell Li_xTiO₂nanoparticles

Abstract: Aiming to improve the hydrogen storage properties of 2LiH + MgB2 (Li-RHC), the effect of the in situ formed and low cost LixTiO2 is investigated.

Cited by 29 publications

References 72 publications

Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches

Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches

Tetrahydroborates: Development and Potential as Hydrogen Storage Medium

Improved kinetic behaviour of Mg(NH2)2-2LiH doped with nanostructured K-modified-LixTiyOz for hydrogen storage

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