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Univ. of Oregon chemists develop liquid-based hydrogen storage material

Ja-2011-08834v_0008
A liquid-phase hydrogen storage material. Credit: ACS, Luo et al. Click to enlarge.

Researchers at the University of Oregon (UO) have developed a boron-nitrogen-based liquid-phase storage material for hydrogen that works safely at room temperature; is both air- and moisture-stable; releases H2 controllably and cleanly at temperatures below or at the proton exchange membrane fuel cell waste-heat temperature of 80 °C; utilizes catalysts that are cheap and abundant for H2 desorption; features reasonable gravimetric and volumetric storage capacity; and does not undergo a phase change upon H2 desorption.

The development of a liquid-phase hydrogen storage material has the potential to take advantage of the existing liquid-based distribution infrastructure, the team notes in their paper published in the Journal of the American Chemical Society.

The appeal of a safe, liquid-phase hydrogen storage material is clear. The US has a network of over 150,000 miles (244,000 km) of pipeline dedicated to delivering liquid petroleum products, and many nations worldwide have similar networks in place. The transition to a hydrogen-based energy economy will be greatly facilitated if it can take advantage of the existing liquid-based distribution channels such as pipelines, tankers, and retail outlets. Two potential liquid-phase hydrogen storage materials that have received recent attention in the literature are formic acid, HCO2H and hydrous hydrazine, N2H4·H2O. One disadvantage of these compounds is that they have decomposition pathways that potentially generate side products that are toxic to fuel cell catalysts (e.g., CO and NH3) in addition to safety concerns (e.g., for hydrazine).

Liquid organic hydrides (i.e., hydrocarbons) are another class of potential hydrogen carriers, but for carbon-rich systems, the hydrogen liberation step is strongly endothermic, typically requiring reaction temperatures of 350–500 °C, well above the “waste heat” temperature of 80—90 °C provided by a standard proton exchange membrane (PEM) fuel cell.

...we disclose herein the development of BN-methylcyclopentane (1), which is an air- and moisture-stable liquid at room temperature. We report that 1 is capable of releasing 2 equiv of H2 per molecule of 1 (4.7 wt %) both thermally, at temperatures above 150 °C, and catalytically using a variety of cheap and abundant metal halides, at temperatures below 80°C.

—Luo et al.

The team, led by team Shih-Yuan Liu, professor of chemistry and researcher in the UO Material Sciences Institute, originally discovered six-membered cyclic amine borane materials that readily trimerize—form a larger desired molecule—with the release of hydrogen. These initial materials, however, were solids. By tweaking the structure, including reducing the ring size from a 6- to a 5-membered ring, the group succeeded in creating a liquid version that has low vapor pressures and does not change its liquid property upon hydrogen release.

Challenges to move this storage platform forward, researchers cautioned, are the needs to increase hydrogen yield and developing a more cost- and energy-efficient regeneration procedure.

Initially, the new platform could be more readily adopted for use in portable fuel cell-powered devices, said Liu, who also is a member of Oregon BEST (Built Environment & Sustainable Technologies Center).

Resources

  • Wei Luo, Patrick G. Campbell, Lev N. Zakharov, and Shih-Yuan Liu (2011) A Single-Component Liquid-Phase Hydrogen Storage Material. Journal of the American Chemical Society doi: 10.1021/ja208834v

Comments

HealthyBreeze

I appreciate that they candidly mention they need to further improve H2 storage yield and the energy efficiency of reversing the process...but could that at least tell us if it is better than current solid hydrate storage density or efficiency? Better still, tell us what percentage of the liquid mass is H2 and what the current conversion losses are.

Roy_H

I agree, it would be much nicer to have more figures to work with. I believe that 4.7% is weight of H2 vs liquid storage. So to store 4kg of H2 would be 85kg of fuel. This is more than acceptable and seems to be close to gasoline in terms of energy density.

Davemart

This compares favourably by weight with other methods of hydrogen storage such as compressing it in a carbon fibre tank or using hydrides:
http://www.ukerc.ac.uk/support/tiki-download_file.php?fileId=1494

Scott

Cella Energy achieved something similar a year ago:

http://cellaenergy.com/

Henry Gibson

Fuel cells are not yet economical without the direct subsidies. And the cost of hydrogen production makes the devices also costly to operate.

The Innas NOAX free piston hydraulic pump engine can have very high compression with the associated very high efficiencies and can also have a Rankine bottom cycle for more efficiency if needed. Any fuel can be used including compression ignition of methane or hydrogen. The high cost of hydrogen production eliminates the benefit of high efficiency especially if cogeneration is used.


The air bearing turbine is sufficiently magic to operate withou any other lubrication ever. The efficiency is high enough when using natural gas to make a hydrogen fuel cell seem very expensive indeed. ..HG..

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