Development of catalytically enhanced sodium aluminum hydride as a hydrogen-storage material

Abstract

The dehydriding of sodium aluminum hydride, NaAlH4, is kinetically enhanced and rendered reversible in the solid state upon doping with selected titanium compounds. Following the initial reports of this catalytic effect, further kinetic improvement and stabilization of the cyclable hydrogen capacity have been achieved upon variation in the method of the introduction of titanium and particle-size reduction. Rapid evolution of 4.0-wt % hydrogen at 100°C has been consistently achieved for several dehydriding/rehydriding cycles. An improved, 4.8-wt % cyclable capacity has been observed in the material doped with a combination of Ti and Zr alkoxide complexes. Doping the hydride with Ti(OBun)4 and Fe(OEt)2 also produces a synergistic effect, resulting in materials that can be rehydrided to 4 wt % at 104°C and 87 atm of hydrogen within 17h. The improved kinetics allowed us to carry out constant-temperature, equilibrium-pressure studies of NaAlH4 that extended to temperatures well below the melting point of the hydride. The 37-kJ/mol value determined for enthalpy of the dehydriding of NaAlH4(s) to Na3AlH6 and Al and the hydrogen plateau pressure of 7 atm at 80°C are in line with the predictions of earlier studies. The nature of the active catalyst and the mechanism of catalytic action are unknown. The catalytically enhanced hydrides appear to be strong candidates for development as hydrogen carriers for onboard proton exchange membran (PEM) fuel cells. However, further research and development in the areas of rehydriding catalysts, large-scale, long-term cycling, safety and adjustment of the plateau hydrogen pressure associated with dehydriding of AlH-6 are required before these materials can be utilized in commercial onboard hydrogen-storage systems.