Influence of Synthesis Gas Components on Hydrogen Storage Properties of Sodium Aluminum Hexahydride

A systematic study of different ratios of CO, CO2, N2 gas components on the hydrogen storage properties of the Na3AlH6 complex hydride with 4 mol% TiCl3, 8 mol% aluminum and 8 mol% activated carbon is presented in this paper. The different concentrations of CO and CO2 in H2 and CO, CO2, N2 in H2 mixture were investigated. Both CO and CO2 gas react with the complex hydride forming Al oxy-compounds, NaOH and Na2CO3 that consequently cause serious decline in hydrogen storage capacity. These reactions lead to irreversible damage of complex hydride under the current experimental condition. Thus, after 10 cycles with 0.1 vol % CO + 99.9 vol %H2 and 1 vol % CO + 99 vol %H2, the dehydrogenation storage capacity of the composite material decreased by 17.2% and 57.3%, respectively. In the case of investigation of 10 cycles with 1 vol % CO2 + 99 vol % H2 gas mixture, the capacity degradation was 53.5%. After 2 cycles with 10 vol % CO +90 vol % H2, full degradation was observed, whereas after 6 cycles with 10 vol % CO2 + 90 vol % H2, degradation of 86.8% was measured. While testing with the gas mixture of 1.5 vol % CO + 10 vol % CO2 + 27 vol % H2 + 61.5 vol % N2, the degradation of 94% after 6 cycles was shown. According to these results, it must be concluded that complex aluminum hydrides cannot be used for the absorption of hydrogen from syngas mixtures without thorough purification.

Electrolyte-Assisted Hydrogen Cycling in Lithium and Sodium Alanates at Low Pressures and Temperatures

An investigation of electrolyte-assisted hydrogen storage reactions in complex aluminum hydrides (LiAlH4 and NaAlH4) reveals significantly reduced reaction times for hydrogen desorption and uptake in the presence of an electrolyte. LiAlH4 evolves ~7.8 wt% H2 over ~3 h in the presence of a Li-KBH4 eutectic at 130 °C compared to ~25 h for the same material without the electrolyte. Similarly, NaAlH4 exhibits 4.8 wt% H2 evolution over ~4 h in the presence of a diglyme electrolyte at 150 °C compared to 4.4 wt% in ~15 h for the same material without the electrolyte. These reduced reaction times are composed of two effects, an increase in reaction rates and a change in the reaction kinetics. While typical solid state dehydrogenation reactions exhibit kinetics with rates that continuously decrease with the extent of reaction, we find that the addition of an electrolyte results in rates that are relatively constant over the full desorption window. Fitting the kinetics to an Avrami-Erofe’ev model supports these observations. The desorption rate coefficients increase in the presence of an electrolyte, suggesting an increase in the velocities of the reactant-product interfaces. In addition, including an electrolyte increases the growth parameters, primarily for the second desorption steps, resulting in the observed relatively constant reaction rates. Similar effects occur upon hydrogen uptake in NaH/Al where the presence of an electrolyte enables hydrogenation under more practical low temperature (75 °C) and pressure (50 bar H2) conditions.

Solution-processed aluminum metals using liquid-phase aluminum-hydrides

Liquid-to-metal Al conversion in liquid aluminum-hydride compounds