Correlation between thermodynamical stabilities of metal borohydrides and cation electronegativites: First-principles calculations and experiments
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- 30 June 2006
- journal article
- research article
- Published by American Physical Society (APS) in Physical Review B
- Vol. 74 (4), 045126
- https://doi.org/10.1103/PhysRevB.74.045126
Abstract
The thermodynamical stabilities for the series of metal borohydrides M(BH4)(n) (M=Li, Na, K, Cu, Mg, Zn, Sc, Zr, and Hf; n=1-4) have been systematically investigated by first-principles calculations. The results indicated that an ionic bonding between Mn+ cations and [BH4](-) anions exists in M(BH4)(n), and the charge transfer from Mn+ cations to [BH4](-) anions is a key feature for the stability of M(BH4)(n). A good correlation between the heat of formation Delta H-boro of M(BH4)(n) and the Pauling electronegativity of the cation chi(P) can be found, which is represented by the linear relation, Delta H-boro=248.7 chi(P)-390.8 in the unit of kJ/mol BH4. In order to confirm the predicted correlation experimentally, the hydrogen desorption reactions were studied for M(BH4)(n) (M=Li, Na, K, Mg, Zn, Sc, Zr, and Hf), where the samples of the later five borohydrides were mechanochemically synthesized. The thermal desorption analyses indicate that LiBH4, NaBH4, and KBH4 desorb hydrogen to hydride phases. Mg(BH4)(2), Sc(BH4)(3), and Zr(BH4)(4) show multistep desorption reactions through the intermediate phases of hydrides and/or borides. On the other hand, Zn(BH4)(2) desorbs hydrogen and borane to elemental Zn due to instabilities of Zn hydride and boride. A correlation between the desorption temperature T-d and the Pauling electronegativity chi(P) is observed experimentally and so chi(P) is an indicator to approximately estimate the stability of M(BH4)(n). The enthalpy change for the desorption reaction, Delta H-des, is estimated using the predicted Delta H-boro and the reported data for decomposed product, Delta H-hyd/boride. The estimated Delta H-des show a good correlation with the observed T-d, indicating that the predicted stability of borohydride is experimentally supported. These results are useful for exploring M(BH4)(n) with appropriate stability as hydrogen storage materials.This publication has 44 references indexed in Scilit:
- Reversible hydrogen decomposition of KAlH4Journal of Alloys and Compounds, 2003
- Effect of Ti-catalyst content on the reversible hydrogen storage properties of the sodium alanatesJournal of Alloys and Compounds, 2002
- X-ray diffraction studies of titanium and zirconium doped NaAlH4: elucidation of doping induced structural changes and their relationship to enhanced hydrogen storage propertiesJournal of Alloys and Compounds, 2002
- Enhancing low pressure hydrogen storage in sodium alanatesJournal of Alloys and Compounds, 2002
- Development of catalytically enhanced sodium aluminum hydride as a hydrogen-storage materialApplied Physics A, 2001
- Metal-doped sodium aluminium hydrides as potential new hydrogen storage materialsJournal of Alloys and Compounds, 2000
- In-situ X-ray diffraction study of the decomposition of NaAlH4Journal of Alloys and Compounds, 2000
- Hydrogenation properties of complex alkali metal hydrides fabricated by mechano-chemical synthesisJournal of Alloys and Compounds, 1999
- Hydrogen cycling behavior of zirconium and titanium–zirconium-doped sodium aluminum hydrideJournal of Alloys and Compounds, 1999
- Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materialsJournal of Alloys and Compounds, 1997