Statistical Thermodynamics of Phase Transformations in Lithium Alanates with Release of Hydrogen

Abstract

Based on the molecular and kinetic concepts, the paper presents the theory of phase transformations in lithium alanates with the release of hydrogen. The calculations are given for free energies of phases and their dependences on pressure, temperature, hydrogen concentration, and energy parameters are determined. The equations are derived for the thermodynamically-equilibrium states which determine the Pressure-Temperature-Concentration diagram and estimate the energy parameters with the use of experimental results taken from the literature. The investigation of the detected temperature/concentration dependence in crystals shows the impossibility of a complete hydrogen release from alanates. The paper contains isotherm and isopleth plots. A possibility is established for the hysteresis effect. A comparison is given to the theoretical and experimental results.