New Foundations of Newman’s Theory for Solid Electrolytes: Thermodynamics and Transient Balances

Newman’s developments of electrochemical thermodynamics and transport phenomena are extendedto account for changes in elastic or plastic deformation stress, as well as for varying pressure,temperature, and composition. The material, momentum, energy, and entropy balances fromconcentrated-solution transport theory are modified to include extended underpinning thermodynamicrelationships. Various colligative properties describing electrolytic materials at equilibriumare identified through analysis of the Gibbs function, which also gives rise to state equations forvolume, deformation strain, and entropy. A dynamical analysis on the continuum scale producesmultiphysical versions of the equation of motion and the heat equation. The discussion concludeswith a statement of the second law from the perspective of irreversible thermodynamics, whichprovides a basis for the future development of transport constitutive laws