Polyaniline and CN-functionalized polyaniline as organic cathodes for lithium and sodium ion batteries: a combined molecular dynamics and density functional tight binding study in solid state.

We present the first atomistic-scale simulation of the discharge process of polymeric cathode materials for electrochemical batteries in solid state. The oxidation of polyaniline (PANI) and of cyano groups (CN) functionalized PANI induced by coordination to the electrolyte anions is computed and voltage curves are estimated. To deal with the large required numbers of atoms and structures, a combination of molecular dynamics and density functional tight binding (DFTB) is used. The DFTB is benchmarked to density functional theory (DFT) calculations using different functionals to confirm its accuracy. The voltages computed with the solid state model are in good agreement with available experimental data and ab initio models based on oligomers. The solid state model also predicts substantially increased voltage with PANI functionalized with cyano groups.