LiBH4 has gained much attention as a potential hydrogen storage material due to its high hydrogen storage capacity of 18.5 wt%. However, LiBH4 only releases its full hydrogen capacity at temperatures greater than 600 degrees C and requires hydrogen pressures of at least 350 bar to rehydrogenate the end products. The dehydrogenation temperature can be altered by thermodynamic tuning through the addition of a reactive agent resulting in a lower enthalpy of dehydrogenation. Most multicomponent hydride systems display dehydrogenation temperatures above 300 degrees C, making them less desirable for automotive applications. In this work we report the solid-state decomposition of LiBH4 in the 2LiBH(4):CaNi5 system below the LiBH4 melting temperature of 270 degrees C. In situ neutron diffraction measurements confirmed the decomposition took place in the solid state at 200 degrees C, forming LiD, CaD2, Ni3B and Ni2B phases as end products. The solid-state decomposition was further supported by SEM and TEM measurements showing the presence of nano-crystalline particles. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.