We present in this work a new formalism for the rapid and accurate evaluation of the thermodynamic properties of compounds and solid solution end-members which are required in the high-throughput computational thermochemistry discovery of new materials. The method is based on the Debye approximation and is fully thermodynamically self-consistent. It considers several energetic contributions, such as the vibrational free energy (including both implicit and explicit anharmonicity), the defect-free energy (via the introduction of thermal vacancies), the energetic effect of thermal excitation of electrons (for metallic solids) as well as other excess terms to precisely reproduce experimental data. Sets of fully self-consistent pressure- and temperature-dependent thermodynamic properties are evaluated from the exact differentiation of this complete free energy formalism. This strategy allows the formalism to be fully integrated in the CALPHAD framework for the development of large thermodynamic databases of both stable and metastable compounds which may form in multicomponent/high-order systems. An emphasis is put in this work on the analysis and precise description of anharmonic vibrational contributions. Finally, sets of self-consistent thermodynamic and thermo-physical properties have been predicted as a function of temperature and compared with both experiments and classical QHA for pure elements (i.e. Ag, Li, V, Al, and C) and stoichiometric compounds of different chemical nature (i.e. MgO, CaO, Al2O3, NaCl, LiFePO4 and InP). The impact of various input parameters of the formalism on the free energy and the derived thermodynamic properties for these solids is analyzed. A better predictive capability and the enhanced flexibility of the proposed formalism are demonstrated.