First-Principles Calculation of the Cu-Li Phase Diagram

Abstract

We present first-principles calculations of the solid-state portion of the Cu-Li phase diagram based on the cluster expansion formalism coupled with the use of (i) bond length-dependent transferable force constants and lattice dynamics calculations to model of vibrational disorder and (ii) lattice gas Monte Carlo simulations to model configurational disorder. These calculations help settle the existence of additional phases in the Cu-Li phase diagram that have been postulated, but not yet clearly established. Our calculations predict the presence of at least one additional phase and the associated predicted phase transitions are consistent with our electrochemical measurements, which exhibit clear plateaus in the electromotive force-composition curve.