Improved de/hydrogenation properties and favorable reaction mechanism of CeH2 + KH co-doped sodium aluminum hydride

•Co-doping CeH2 + KH can improve the hydrogen storage property of NaAlH4 markedly.•0.98NaH/Al + 0.02CeCl3/0.02KH composite shows the best hydrogen storage property.•Thermodynamics and kinetics of NaAlH4 are improved by Co-doping with CeH2 + KH.•Dehydrogenation of composite is conformed to phase-boundary growth mechanism.

Sodium aluminum hydride (NaAlH4) was directly synthesized by ball milling NaH/Al co-doped with CeCl3 + KH under a hydrogen pressure of 3 MPa at room temperature. Out of various samples corresponding to xNaH/Al + 0.02CeCl3 + yKH (x + y = 1; y = 0, 0.02, 0.04 mol%) composites, the composite with y = 0.02 exhibits the optimum de/hydrogenation properties. It shows that the addition of KH can effectively improve the dehydrogenation properties of second step reaction of NaAIH4 system. The composite with y = 0.02 starts to release hydrogen from 87 °C and completes dehydrogenation within 20 min at 170 °C, with good cycling de/hydrogenation kinetics at relatively lower temperature (100–140 °C). After ball milling, the CeCl3 precursor can be changed into CeH2 catalytic active component in the first several de/hydrogenation cycles. Apparent activation energy of the second decomposition step of NaAIH4 system can be effectively decreased by addition of KH, resulting in the decrease of desorption temperatures. Based on the microstructure analyses combined with hydrogen storage performances, the improved dehydrogenation properties of sodium aluminum hydride system are ascribed to the lattice volume expansion of Na3AlH6 during the dehydrogenation process resulted from the addition of KH. Moreover, by analyzing the reaction kinetics of CeCl3 + KH co-doped sample, both of the decomposition steps of composite with y = 0.02 were conformed to the two-dimension phase-boundary growth mechanism. The mechanistic investigations gained here could help to understand the de/rehydrogenation behaviors of catalyzed complex metal hydride systems.

Graphical abstractSodium aluminum hydride (NaAlH4) was directly synthesized by ball milling NaH/Al co-doped with CeCl3 + KH under a hydrogen pressure of 3 MPa at room temperature. It was found that the addition of KH can effectively improve the dehydrogenation properties of second step reaction. Among different composites, 0.98NaH/Al + 0.02CeCl3/0.02KH shows the best de/hydrogenation properties, and both of the dehydrogenation steps of 0.98NaH/Al + 0.02CeCl3/0.02KH composite were conformed to two-dimension phase-boundary growth mechanism.Figure optionsDownload full-size imageDownload as PowerPoint slide