Computational\nInsights into Electrolyte-Dependent\nLi-Ion Charge-Transfer Kinetics at the Li<sub><i>x</i></sub>CoO<sub>2</sub> Interface

Interface engineering remains a largely underexplored\narea, and\nyet it holds the keys to high-performance Li-ion batteries. It is\nthe charge transfer across electrode–electrolyte interfaces,\nits inefficient energetics, and sluggish kinetics that are oftentimes\nsignificant obstacles for achieving fast charging and high power regimes\nwithout compromising battery lifespan. This work propose a Boltzmann-averaged\nfirst-principles workflow based on constant potential and constrained\ndensity functional theory for estimation of atomic scale factors influencing\ncoupled ion-electron charge transfer kinetics across battery electrode–electrolyte\ninterfaces. The approach estimates diabatic Li⁺ interface\nenergy landscapes as a function of the interface character and operational\nconditions, needed to simulate charging/discharging currents. Experimental\ntrends for the Li_<i>x</i>CoO₂ (0.5\n≤ <i>x</i> ≤ 1.0) electrode in varied organic\nelectrolytes with LiPF₆ and LiClO₄ salts are\nreproduced, identifying Li⁺ transfer energy and Li⁺ adsorption energy as decisive factors influencing the enhanced\nkinetics in LiClO₄-based electrolytes over LiPF₆, rationalized by a stronger surface interaction of ClO₄^–