First, to simulate the cathode half-cell, models of the LixCoO2-electrolyte interface with x = {0.50, 0.75, 1.00} are created from the rhombohedral (R3 ̅ m) LiCoO2 scaffold structure, i.e., assuming topotactical (de)lithiation. The LCO surface is represented by a periodic (1, 2/3; 0, 4) supercell model of the (101 ̅ 4) facet, which is a commonly observed and low energy surface. (101 ̅ 4) exposes Li-ion transport channels that can exchange Li + with the electrolyte (illustrated in Scheme 1). Consistent with early battery cycles, Second, charge transfer properties (vide infra) associated with the interface models are computed using constrained DFT (cDFT) to ensure that the charge state is fixed at the LCO interface. cDFT is combined with constant potential DFT, where the electrode potential corresponds to the reversible potential (i.e., the open circuit voltage, OCV, when referenced to Li/Li + ) of the LCO half-cell at the given SOC. A graphene layer beneath the surface slab model acts as electron reservoir (i.e., a computational charge collector), ensuring a continuous variation of the Fermi level (and thereby the potential) of the cell as electrons are added or subtracted. Using the constant potential scheme, the free energy landscape can be sampled at the same conditions facilitating fair comparison between states. Unless otherwise specified, these calculations are carried out in VASP (version 6.3.2) using the PBE-D3(BJ) level of theory and standard PAW core potentials. To account for both directional and long-range solvation effects, hybrid explicit-implicit solvation models are employed with the implicit part represented by VASPsol 60,61 using a dielectric constant of 20 corresponding to a 3:7 EC/EMC mixture. Third, to evaluate the electrode current density (i CIET ) at varied interface properties and overpotential,