Ammonia-Borane Complex for Hydrogen Storage PIs: N. Mohajeri, A. T-Raissi, K. Ramasamy, O. Adebiyi, and G.

Bokerman (Florida Solar Energy Center)

Research Period: June 2002 to December 2007 Summary The goal of this project was to develop a high-density hydrogen storage system based on ammonia borane (AB) complex. Due to their high hydrogen capacity, AB hydrides have been employed as disposable hydrogen (H2) sources for fuel cell applications. The objectives of this project were to 1) identify viable amine-borane (AB) complexes for hydrogen storage at ambient conditions, and 2) develop a cost-effective synthetic route for hydrogenation of borazine to cyclotriborazane - as a means of chemical hydrogen storage. Ammonia borane (AB) complex is a chemical hydride that is stable in air and water, and contains very high hydrogen content (19.6 wt%) with a system-level H2 energy storage density of about 2.74 kWh/L (vs. 2.36 kWh/L for a liquid hydrogen Dewar). AB is a promising material as a hydrogen carrier especially for power generation utilizing proton exchange membrane fuel cells (PEMFC). Release of hydrogen in the AB complex can occur by either thermolysis or hydrolysis. Thermolysis of AB generates, in addition to hydrogen, species such as borazine, monomeric aminoborane, and diborane. In the case of AB hydrolysis, ammonia is the byproduct of the reaction. The results have shown the liberation of 2 moles of hydrogen by thermolysis of AB complex with relatively minor expenditure of energy. Without downstream treatment, some quantities of borazine and poly-aminoborane are also generated. The results have also shown that borazine generated can be effectively captured and removed from H2 gas stream using a broad class of solid sorbents including carbons and mesoporous silica. Results for pyrolysis of the AB complex have shown it to be an overall exothermic process that requires induction energy to initiate AB decomposition until about 0.3 moles of H2 is released. At this point, the reaction is self sustaining and proceeds to completion with the additional release of 2 moles of hydrogen gas. Induction energy required to release 2 moles of H2 is about 16.2 kJ/mol of AB or 8.1 kJ/mol of H2,

which corresponds to 3.35% of the chemical energy of hydrogen generated (on LHV basis). Near room temperature hydrolysis of AB complex has been carried out using small amounts of K2PtCl6 salt. The AB hydrolytic reaction is exothermic and can be extremely fast, kinetically. The report also measures the thermal conductivities of composites formed by mixing fine aluminum powder with AB complex at temperatures in the range of 300-420K. At 300 K, the thermal conductivity of pure AB is approximately 15 W/m-K. A composite pellet prepared by mixing 10% by weight aluminum powder with AB complex had a thermal conductivity that was a factor of 4 higher than that of pure AB.