Improved reversible hydrogen storage of LiAlH4 by nano-sized TiH2

Liu, Shu-Sheng; Li, Zhibao; Jiao, Chengli; Si, Xiaoliang; Yang, Lini; Zhang, Jian; Zhou, Huaiying; Huang, Fenglei; Gabélica, Z.; Schick, Christoph; Sun, Lixian; Xu, Fen

doi:10.1016/j.ijhydene.2012.11.042

Cited by 43 publications

(20 citation statements)

References 40 publications

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“…The most conclusive evidence for the reversible H 2 uptake and release from LiAlH 4 @NCMK-3 was obtained from MAS NMR, a technique which provides information about all species present in the sample, including the amorphous ones. Typical 27 Al MAS NMR peaks for the tetrahedral Al in LiAlH 4 are observed at 98 ppm in both as-synthesized LiAlH 4 @NCMK-3 and LiAlH 4 @CMK-3 indicating successful hydride incorporation (Fig. 3c-e).…”

Section: Hydrogen Desorption and Absorptionmentioning

confidence: 93%

“…2a). In addition, we rule out the possibility that the second release is the decomposition of Li 3 AlH 6 because there are no indications of a stable intermediate Li 3 AlH 6 phase, including the highly sensitive 27 Al MAS NMR technique. This con rms the prediction that the H 2 desorption of LiAlH 4 nanoparticles in LiAlH 4 @NCMK-3 bypasses the stable Li 3 AlH 6 phase.…”

Section: Origin Of Reversibility and Altered Reaction Pathwaymentioning

confidence: 99%

“…Prior to each measurement, the reactor was evacuated, and the volume was calibrated using He gas. Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) measurements were collected using a triple resonance probe on a 600 MHz (14 T) Bruker Biospin Avance III, operating at 156.37 and 233.24 MHz for 27 Al and 7 Li, respectively. Additional details on the speci cs of MAS NMR measurements are provided in the SI (Supplementary note 3).…”

Section: Characterizationmentioning

confidence: 99%

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Reversing the Irreversible: Thermodynamic Stabilization of Lithium Aluminum Hydride Nanoconfined Within a Nitrogen-Doped Carbon Host

Cho

Snider

et al. 2021

Preprint

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A general problem when designing functional nanomaterials for energy storage is the lack of control over the stability and reactivity of metastable phases. Using the high-capacity hydrogen storage candidate LiAlH4 as an exemplar, we demonstrate a new approach to thermodynamic stabilization of metastable metal hydrides by coordination to nitrogen binding sites within the nanopores of N-doped CMK-3 carbon (NCMK-3). The resulting LiAlH4@NCMK-3 material releases H2 at temperatures as low as 126 °C with full decomposition below 240 °C, bypassing the usual Li3AlH6 intermediate. Moreover, >80% of LiAlH4 can be regenerated under 100 MPa H2, a feat previously thought to be impossible. The nitrogen sites lower the energy barrier for regenerating the hydride by changing the density of states in the vicinity of the Fermi level, effectively acting as solvation sites for lithium ions. Theoretical calculations provide a rationale for the unprecedented solid-state reversibility, which derives from the combined effects of nanoconfinement, Li adatom formation, and charge redistribution between the metal hydride and the host.

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Section: Hydrogen Desorption and Absorptionmentioning

confidence: 93%

Section: Origin Of Reversibility and Altered Reaction Pathwaymentioning

confidence: 99%

Section: Characterizationmentioning

confidence: 99%

See 1 more Smart Citation

Reversing the Irreversible: Thermodynamic Stabilization of Lithium Aluminum Hydride Nanoconfined Within a Nitrogen-Doped Carbon Host

Cho

Snider

et al. 2021

Preprint

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“…Nevertheless, many efforts have been devoted to solve the crucial LiAlH 4 drawbacks for practical applications, corresponding to high thermodynamic stability and slow desorption kinetics by doping various catalysts. To date, the documented catalysts for LiAlH 4 fall into six categories: (1) elemental metal, such as Ni, 7,8 Fe, 7,9,10 V, 7,14 Sc, 14 and Ti; 7,10−14 (2) (6) and others, such as nanosized TiH 2 , 33 Ce(SO 4 ) 2 , 34 VCl 3 and CNFs, 15 SWCNT-metallic, 35 and TiN. 4 Most of these catalysts do not work with LiAlH 4 as a suitable hydrogen-storage medium.…”

Section: Introductionmentioning

confidence: 99%

NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties

Zhai

et al. 2013

J. Phys. Chem. C

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The effects of NiFe 2 O 4 nanoparticles addition on the dehydrogenation behavior of LiAlH 4 were investigated. The onset dehydrogenation temperature for LiAlH 4 +3 mol % NiFe 2 O 4 sample is 61°C, which decreased by 94°C compared with the as-received LiAlH 4 and released ∼7.2 wt % hydrogen when heated to 180°C. Isothermal desorption measurements show that the 3 mol % NiFe 2 O 4 -doped sample releases ∼7.0 wt % of hydrogen in 91 min at 120°C, which is 6.3 wt % higher than the as-received LiAlH 4 under the same conditions. Through calculating the apparent activation energy of the LiAlH 4 samples with and without NiFe 2 O 4 for the first two dehydrogenation stages, the E a of the LiAlH 4 +3 mol % NiFe 2 O 4 sample is 54.3 and 70.8 kJ/mol, resulting in 52.5 and 59% decrease, respectively, compared with the as-received LiAlH 4 . Analyzing the X-ray diffraction and Fourier transform infrared spectroscopy results, it is reasonable to believe that the remarkable improvement of dehydrogenation properties of NiFe 2 O 4 -doped LiAlH 4 results from the in situ formed LiFeO 2 and Al−Ni compounds, providing the active sites for nucleation and growth of the dehydrogenation products.

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“…The species of Al 3 Ti is also notorious in facilitating the dissociation of molecular hydrogen and its recombination on surfaces, thus reducing the hydrogen storage operating temperature of metal and complex hydrides, along with Ti‐based additives 73,74 . Additionally, several studies have found that doping TiH 2 to LiAlH 4 or MgH 2 remarkably improves the hydrogen sorption properties 75,76 . Hence, the in situ formed decomposition products of MgF 2 , LiF, Al 3 Ti and TiH 2 , coupled with the chemical reactions occurred, shall generate a synergetic catalytic role that significantly enhances the hydrogen sorption performance of the 2LiAlH 4 + Mg(BH 4 ) 2 system.…”

Section: Resultsmentioning

confidence: 99%

Improved hydrogen storage performances of LiAlH ₄ + Mg( BH ₄ ) ₂ composite with TiF ₃ addition

et al. 2020

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Summary This paper studies on the preparation of the alanate‐borohydride combined system, LiAlH4 + Mg(BH4)2 with diverse molar ratios (1:1, 1:2, and 2:1) using the ball milling technique. The findings show that there is a mutual destabilization between the hydrides where the newly combined system has superior hydrogen storage performances as opposed to the unary components (LiAlH4 and Mg[BH4]2). Analysis on the initial decomposition temperature and isothermal de/hydrogenation kinetics has proven that the 2LiAlH4 + Mg(BH4)2 system possesses better performance. In an endeavor to ameliorate the performances of the hydrogen storage of 2LiAlH4 + Mg(BH4)2, the destabilized system was doped with TiF3. Three major steps of desorption were detected during the heating process in the 2LiAlH4 + Mg(BH4)2 system with and without the addition of TiF3, which are correlated to the decomposition of Mg(AlH4)2, MgH2 and LiBH4. It is found that 2LiAlH4 + Mg(BH4)2 + 5 wt.% TiF3 has decreased the initial decomposition temperature at about 60°C, which is 55°C lower than the non‐catalyzed 2LiAlH4 + Mg(BH4)2 system. The isothermal absorption/desorption kinetics of the 2LiAlH4 + Mg(BH4)2 system have also been enhanced by the addition of TiF3. The activation energy for Mg(AlH4)2‐, MgH2‐, and LiBH4‐relevant decomposition after doped 2LiAlH4 + Mg(BH4)2 with TiF3 are reduced to 36.5, 23.3, and 17.6 kJ mol−1. Studies on the structural characteristics analysis of the 2LiAlH4 + Mg(BH4)2 + TiF3 sample hint to the fact that the formation of the MgF2, LiF, TiH2 and Ti‐Al species, during desorption, is the main responsible factor for the observed thermodynamics change of the reactions by modifying the dehydrogenation and hydrogenation pathway. The catalytic role played by TiF3 may have encouraged the interaction between Mg(AlH4)2, MgH2, and LiBH4, further ameliorate the de/hydrogenation of the 2LiAlH4 + Mg(BH4)2 + TiF3 destabilized system.

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Improved reversible hydrogen storage of LiAlH4 by nano-sized TiH2

Cited by 43 publications

References 40 publications

Reversing the Irreversible: Thermodynamic Stabilization of Lithium Aluminum Hydride Nanoconfined Within a Nitrogen-Doped Carbon Host

Reversing the Irreversible: Thermodynamic Stabilization of Lithium Aluminum Hydride Nanoconfined Within a Nitrogen-Doped Carbon Host

NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties

Improved hydrogen storage performances of LiAlH ₄ + Mg( BH ₄ ) ₂ composite with TiF ₃ addition

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Improved reversible hydrogen storage of LiAlH4 by nano-sized TiH2

Cited by 43 publications

References 40 publications

Reversing the Irreversible: Thermodynamic Stabilization of Lithium Aluminum Hydride Nanoconfined Within a Nitrogen-Doped Carbon Host

Reversing the Irreversible: Thermodynamic Stabilization of Lithium Aluminum Hydride Nanoconfined Within a Nitrogen-Doped Carbon Host

NiFe2O4 Nanoparticles Catalytic Effects of Improving LiAlH4 Dehydrogenation Properties

Improved hydrogen storage performances of LiAlH 4 + Mg( BH 4 ) 2 composite with TiF 3 addition

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NiFe₂O₄ Nanoparticles Catalytic Effects of Improving LiAlH₄ Dehydrogenation Properties

Improved hydrogen storage performances of LiAlH ₄ + Mg( BH ₄ ) ₂ composite with TiF ₃ addition