In this work, we develop a computational workflow based on CIET theory combined with constrained and constant potential DFT (Scheme 1) for analysis of the electronic and molecular properties that influence the IT and ET contributions to interface charge transfer resistance. The modeling approach complements previous efforts that sample the free energy landscape of battery interfaces using classical MD simulations, which focused on IT but neglects ET. The approach also extends on earlier first-principles work on battery interface kinetics by accounting for electrode bias as well as the coupled transfer of ions and electrons. By employing constant potential DFT, the approach ensures that the reaction landscape is explored under equal conditions as the addition/removal of ions from a finite model surface otherwise gives rise to spurious fluctuations of the electron chemical potential, associated with noisy or biased results. Recent work on the LiFePO4 and LiCoO2 cathodes has, in addition, found that CIET models represents experimental data better than models that only reflect ET or IT. From constrained DFT, it is possible to sample the reaction landscape for the reduced and oxidized charge states separately allowing for the evaluation of the diabatic energy profiles needed to obtain the chargetransfer parameters used in CIET. Using our framework, we can thus move closer to simulating realistic battery conditions, including accounting for simultaneous ET and IT, but also by emulating electrode potential, temperature, and ion concentration. The computational approach is benchmarked by reproducing measured current densities at the state-of-the-art 41 LixCoO2 (LCO) electrode at varied states of charge (SOC; 0.5≤x≤1.0) and as a function of the composition of a liquid organic electrolytes based on ethylene carbonate (EC) and ethyl methyl carbonate (EMC) containing LiPF6 and LiClO4 salts. Our work provides insights into critical aspects towards improved interface kinetics, it explains the faster charge transfer kinetics observed in LiClO4 electrolytes in terms of atomic scale properties, and sets the stage for future searches for battery materials with tailored interface properties.