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Na3AlH6 can be directly formed by mechanical milling NaH/Al with TiF3 under hydrogen atmosphere. The hydrogenation fraction of NaH increases with increasing the milling time, and reaches up to 0.61 after 20 h milling. Thus-formed Na3AlH6 exhibits unexpected polymorphic transformation and decomposition behaviors. This, together with the unusual hydrogen storage performance of the mechanically prepared materials, provides us a suggestive perspective to probe the favorable modification of the thermodynamics of Na3AlH6 and nature of active Ti-species in Ti-doped NaAlH4. (C) 2005 American Institute of Physics.

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