The influence of SWCNT-metallic nanoparticle mixtures on the desorption properties of milled MgH2 powders.

We have examined the effect of single-walled carbon nanotube (SWCNT)-metallic nanoparticle additions on the hydrogen desorption behavior of MgH(2) after high-energy co-milling. The metallic nanoparticles were the catalysts used for the SWCNT growth. The co-milling consisted of high-energy planetary milling in an inert argon environment of the hydride powder mixed with the SWCNTs. Identically milled pure MgH(2) powders were used as a baseline. The composites were tested using a combined differential scanning calorimeter and thermogravimetric analyzer, while the microstructures were examined using a variety of techniques including x-ray diffraction and transmission electron microscopy (TEM). We found that the SWCNT-nanoparticle additions do have an influence on the desorption kinetics. However, the degree to which they are effective depends on the composite's final state. The optimum microstructure for sorption, obtained after 1 h of co-milling, consists of highly defective SWCNTs in intimate contact with metallic nanoparticles and with the hydride. This microstructure is optimum, presumably because of the dense and uniform coverage of the defective SWCNTs on the MgH(2) surface. Prolonged co-milling of 7 h destroys the SWCNT structure and reduces the enhancement. Even after 72 h of co-milling, when the SWCNTs are completely destroyed, the metallic nanoparticles remain dispersed on the hydride surfaces. This indicates that the metallic nanoparticles alone are not responsible for the enhanced sorption and that there is indeed something catalytically unique about a defective SWCNT-metal combination. Cryo-stage TEM analysis of the hydride powders revealed that they are nanocrystalline and in some cases multiply twinned. To our knowledge this is the first study where the structure of milled alpha- MgH(2) has been directly imaged. Since defects are an integral component of hydride-to-metal phase transformations, such analysis sheds new insight regarding the fundamental microstructural origins of the sorption enhancement due to mechanical milling.