The effect of Al on the hydrogen sorption mechanism of LiBH(4).
We demonstrate the synthesis of LiBH(4) from LiH and AlB(2) without the use of additional additives or catalysts at 450 degrees C under hydrogen pressure of 13 bar to the following equation: 2LiH + AlB(2) + 3H(2)<--> 2LiBH(4) + Al. By applying AlB(2) the kinetics of the formation of LiBH(4) is strongly enhanced compared to the formation from elemental boron. The formation of LiBH(4) during absorption requires the dissociation of AlB(2), i.e. a coupled reaction. The observed low absorption-pressure of 13 bar, measured during hydrogen cycling, is explained by a low stability of AlB(2), in good agreement with theoretical values. Thus starting from AlB(2) instead of B has a rather low impact on the thermodynamics, and the effect of AlB(2) on the formation of LiBH(4) is of kinetic nature facilitating the absorption by overcoming the chemical inertness of B. For desorption, the decomposition of LiBH(4) is not indispensably coupled to the immediate formation of AlB(2). LiBH(4) may decompose first into LiH and elemental B and during a slower second step AlB(2) is formed. In this case, no destabilization will be observed for desorption. However, due to similar stabilities of LiBH(4) and LiBH(4)/Al a definite answer on the desorption mechanism cannot be given and neither a coupled nor decoupled desorption can be excluded. At low hydrogen pressures the reaction of LiH and Al gives LiAl under release of hydrogen. The formation of LiAl increases the total hydrogen storage capacity, since it also contributes to the LiBH(4) formation in the absorption process.
Friedrichs
O
O
Empa, Swiss Federal Laboratories for Materials Testing and Research, Department of Environment, Energy and Mobility, Div. Hydrogen and Energy, Uberlandstrasse 129, CH-8600, Dübendorf, Switzerland. oliver.friedrichs@empa.ch
Kim
J W
JW
Remhof
A
A
Buchter
F
F
Borgschulte
A
A
Wallacher
D
D
Cho
Y W
YW
Fichtner
M
M
Oh
K H
KH
Züttel
A
A