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ESRF Researchers Discover Unexpected and Promising New Form of Hydride for Hydrogen Storage

4 December 2007

Esrf1
Crystal structure of the LiBH4 new phase. Click to enlarge. Credits: Andgewandte Chemie.

Scientists at the European Synchrotron Radiation Facility (ESRF) have discovered a new form of lithium borohydride—a material that contains 18 wt% of hydrogen, making it potentially attractive for on-board hydrogen storage in vehicles. The drawback to date of lithium borohydride is that it only releases hydrogen at quite high temperatures (above 300°C).

The team at the ESRF has found a new form of the compound that could possibly release hydrogen in mild conditions. This discovery, completely unexpected from the point of view of theoretical predictions, was published today as a Very Important Paper in Angewandte Chemie.

Researchers at the Swiss-Norwegian experimental stations (beamlines) at the ESRF are currently studying several compounds of light elements with hydrogen and the different forms they take at different pressure and temperature. Lithium borohydride, LiBH4, is one of the compounds they study as it has a high weight content of hydrogen (18%).

The newly discovered form of this compound is promising because it appears to be unstable. Until today, all the known forms of this material are too stable, which means that they don’t let the hydrogen go.

This one is really unexpected and very encouraging.

—Yaroslav Filinchuk, corresponding author

In order to obtain new forms of lithium borohydride, the team applied to the sample pressures up to 200,000 bar. (The pressure of 200,000 bar applied to LiBH4 in the ESRF experiment is about 80 times bigger than the pressure exerted on Earth’s crust by Mount Everest—the latter is roughly equal to 2.5 kbar). Although impressive, this figure is not a record—much higher pressures still can be reached in the lab using the same diamond anvil cell technique, but this was not necessary for this experiment.

Diffraction of synchrotron light was used to determine arrangement of atoms in the resulting materials. In this way two novel structures of lithium borohydride were found. One of them is truly unprecedented and reveals strikingly short contacts between hydrogen atoms.

Combined experimental and theoretical efforts suggest that the new from of LiBH4 can release hydrogen at a lower temperature. Filinchuk explains that “the new form becomes even more attractive considering the fact it appears already at 10,000 bar, the pressure used by pharmaceutical companies to compress pellets.” The authors argue that this form can be stabilized by chemical substitutions even at ambient pressure. For now, the team’s next step is to apply chemical engineering to the compound to “freeze” the new form at ambient conditions and check whether it shows more favorable hydrogen storage properties than pure lithium borohydride.

Despite the fact that hydrogen is not well detected by X-rays in general, scientists managed to see it thanks to the high brilliance of the ESRF synchrotron light. Although theory failed to predict the novel structure, it fully supports this experimental finding. Therefore, this work presents a breakthrough in experimental studies of hydrogen-rich system, explains the failure of the previous theoretical predictions and suggests the novel form of the compound to be instrumental in obtaining improved hydrogen storage materials, according to the authors.

Synchrotron radiation was recently successfully applied to potential hydrogen storage materials and it turns out to be more useful than generally expected for so light systems. The team at the Swiss-Norwegian Beam Lines at the ESRF will continue to exploit and develop this at first glance unexpected union.

Resources

  • Y. Filinchuk, D. Chernyshov, A. Nevidomskyy, V. Dmitriev, “High-Pressure Polymorphism as a Step towards Destabilization of LiBH4Angewandte Chemie Int. Ed., DOI: 10.1002/anie.200704711 (2007)

December 4, 2007 in Hydrogen Storage | Permalink | Comments (11) | TrackBack (0)

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Comments

A lithium nanostructure to store hydrogen....

If we're going to go that far, then why not just create a lithium nanostructured battery?

Why don't they make dilithium crystals? Then we could go beyond where any man has gone before.

Thank you for discovering lithium borohydride. Please let me know when an associated engineering group has created an economical, industrial grade process for manufacturing it in bulk. Until then it's just an interesting idea.

KS: It's more than just making it, we also have to find a way to transport and compress it without consuming a great deal of energy.

Check the site of the European Fuel Cell Forum, efec-dot-com, and look for the page of reports, most authored by Ulf Bossel. He does a very thorough analysis of the prospects of hydrogen fuel cells as a transportation solution.

Oops! That web site is efcf-dot-com. Sorry for the typo!

The other catch.
It requires 572°F before it releases the hydrogen.

How stupid is that?

There's a chance an unstable form of LiBH4 might reduce its energy by turning into the stable form.

Iff a way can be found to produce LiBH4 cheaply, it could be useful for stationary hydrogen storage even at high pressures - though not as high as 10000 bar, let alone 200000. As a way to store hydrogen for fuel in mobile applications, its a non-starter.

The value of this research lies in the improved understanding of the fundamental adsorption and desorption mechanisms involved. Perhaps other compounds will behave in similar ways at pressures and temperatures that are more suitable for real-world applications.

@ Michael Weng -

stop blogspamming. Nobody here is looking to buy your diesel injectors.

Looked into Sodium Borohydride back in 2003 for the same purpose. The real problem lies in the fact that all these concoctions leave a huge tankful of H2-depleted slurry in the tank. It either has to be re-hydrogenated in situ or recycled. In either case it's weight to storage capacity (energy density) is terrible. And it was unable to supply enough on-demand H2 to realistically power a passenger vehicle.

GryFalc has the right idea - nano Li crystals for electron storage.

Look into the MSDS for LiBH4. It does seem to be rather nasty material.
http://www.sciencelab.com/xMSDS-Lithium_Borohydride-9924508

Rafael,
Just for a laugh I went to that Weng sites all 3, and guess what they didnt even show.
But I got some popup add a little later.
Wonder what censorship they are under over there.
Note spam no longer on this page.

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