To facilitate the development of new materials for use in batteries, it is necessary to develop ab initio full-electron computational techniques for modeling potential new battery materials. Here, we tested density functional theory procedures that are accurate enough to obtain the energetics of a zinc/copper voltaic cell. We found the magnitude of the zero-point energy correction to be 0.01-0.2 kcal/mol per atom or molecule and the magnitude of the dispersion correction to be 0.1-0.6 kcal/mol per atom or molecule for Zn n , (H2O) n , [Formula: see text], [Formula: see text], and Cu n . Counterpoise correction significantly affected the values of ∆[Formula: see text], ∆[Formula: see text], and ∆Esolv by 1.0-3.1 kcal/mol per atom or molecule at the B3PW91/6-31G(d) level of theory, but by only 0.04-0.4 kcal/mol per atom or molecule at the B3PW91/cc-pVTZ level of theory. The application of B3PW91/6-31G(d) yielded results that differed from macroscopic experimental values by 0.1-7.1 kcal/mol per atom or molecule, whereas applying B3PW91/cc-pVTZ produced results that differed from macroscopic experimental values by 0.1-4.8 kcal/mol per atom or molecule, with the smallest differences occurring for reactions with a small macroscopic experimental ∆E and the largest differences occurring for reactions with a large macroscopic experimental ∆E, implying size consistency.
Keywords: Battery; Copper; DFT; Nanobattery; Voltaic cell; Zinc.