AbstractThe Lithium–Boron Reactive Hydride Composite System (Li-RHC) (2 LiH + MgB2/2 LiBH4 + MgH2) is a high-temperature hydrogen storage material suitable for energy storage applications. Herein, a comprehensive gas-solid kinetic model for hydrogenation is developed. Based on thermodynamic measurements under absorption conditions, the system's enthalpy ΔH and entropy ΔS are determined to amount to −34 ± 2 kJ∙mol H2−1 and −70 ± 3 J∙K−1∙mol H2−1, respectively. Based on the thermodynamic behavior assessment, the kinetic measurements' conditions are set in the range between 325 °C and 412 °C, as well as between 15 bar and 50 bar. The kinetic analysis shows that the hydrogenation rate-limiting-step is related to a one-dimensional interface-controlled reaction with a driving-force-corrected apparent activation energy of 146 ± 3 kJ∙mol H2−1. Applying the kinetic model, the dependence of the reaction rate constant as a function of pressure and temperature is calculated, allowing the design of optimized hydrogen/energy storage vessels via finite element method (FEM) simulations.