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Prediction of thermodynamically reversible hydrogen storage reactions utilizing Ca–M(M = Li, Na, K)–B–H systems: a first-principles study

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Abstract

Calcium borohydride is a potential candidate for onboard hydrogen storage because it has a high gravimetric capacity (11.5 wt.%) and a high volumetric hydrogen content (∼130 kg m−3). Unfortunately, calcium borohydride suffers from the drawback of having very strongly bound hydrogen. In this study, Ca(BH4)2 was predicted to form a destabilized system when it was mixed with LiBH4, NaBH4, or KBH4. The release of hydrogen from Ca(BH4)2 was predicted to proceed via two competing reaction pathways (leading to CaB6 and CaH2 or CaB12H12 and CaH2) that were found to have almost equal free energies. Using a set of recently developed theoretical methods derived from first principles, we predicted five new hydrogen storage reactions that are among the most attractive of those presently known. These combine high gravimetric densities (>6.0 wt.% H2) with have low enthalpies [approximately 35 kJ/(mol−1 H2)] and are thermodynamically reversible at low pressure within the target window for onboard storage that is actively being considered for hydrogen storage applications. Thus, the first-principles theoretical design of new materials for energy storage in future research appears to be possible.

Calculated van’t Hoff plot for reactions (10-24*) listed in the Ca-M(Li, Na, K)-B-H system (Tables 2–4). The region within the rectangular box corresponds to desirable temperatures and pressures for on-board hydrogen storage PH2 = 1-700 bar and T = 233 to +355 K

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Acknowledgments

This work was supported by the Natural Science Foundation of China (21031003 and 21103101) and the Key Project of Chinese Ministry of Education (no. 212022).

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Authors and Affiliations

  1. School of Chemistry and Materials Science, Shanxi Normal University, Linfen, 041004, China

    Yajuan Guo, Ying Ren, Haishun Wu & Jianfeng Jia

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  1. Yajuan Guo
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Correspondence to Haishun Wu.

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Guo, Y., Ren, Y., Wu, H. et al. Prediction of thermodynamically reversible hydrogen storage reactions utilizing Ca–M(M = Li, Na, K)–B–H systems: a first-principles study. J Mol Model 19, 5135–5142 (2013). https://doi.org/10.1007/s00894-013-2012-8

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  • DOI: https://doi.org/10.1007/s00894-013-2012-8

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