LiAlH4–ZrCl4 mixtures for hydrogen release at near room temperature

Abstract

The dehydrogenation temperature of LiAlH4 was significantly reduced by the production of mixtures with ZrCl4. Stoichiometric 4:1, and 5 mol % mixtures of LiAlH4 and ZrCl4 were produced by ball milling at room temperature and −196 °C, and tested for dehydrogenation at low temperature. Cryogenic ball-milling resulted in an effective way to produce reactive mixtures for hydrogen release; because of achieving small aggregates size (5–20 μm) in 10 min of cryomilling while preventing substantial decomposition during preparation. Dehydrogenation reaction in the mixtures LiAlH4/ZrCl4 started around 31–47 °C under different heating rates. Partial dehydrogenation was proved at 70 °C: 4.4 wt % for the 5 mol% ZrCl4–LiAlH4 mixture, and 3.4 wt % for the best 4:1 stoichiometric mixture. Complete dehydrogenation up to 250 °C released 6.4 wt% and 4.1 wt%, respectively. Dehydrogenation reactions are exothermic, and the LiAlH4/ZrCl4 mixtures are unstable and difficult to handle. The activation energy of the exothermic reactions was estimated as 113.5 ± 9.8 kJ/mol and 40.6 ± 6.6 kJ/mol for 4LiAlH4+ZrCl4 and 5%mol ZrCl4+LiAlH4 samples milled in cryogenic conditions, respectively. The dehydrogenation pathway was changed in the LiAlH4/ZrCl4 mixtures as compared to pure LiAlH4. Dehydrogenation reaction is proposed to form Al, LiCl, Zr, and H2 as main products. Modification of the dehydrogenation reaction of LiAlH4 was achieved at the cost of reducing the total hydrogen release capacity.