Computational Insights into Electrolyte-Dependent Li-Ion Charge-Transfer Kinetics at the Li <sub> <i>x</i> </sub> CoO <sub>2</sub> Interface
Joakim Halldin Stenlid, Pjotrs Žguns, Daniele Vivona, Abhishek Aggarwal, Kiarash Gordiz, Yirui Zhang, Shakul Pathak, Martin Z. Bazant, Yang Shao‐Horn, Artem Baskin, John W. Lawson
Abstract
Interface engineering remains a largely underexplored area, and yet it holds the keys to high-performance Li-ion batteries. It is the charge transfer across electrode–electrolyte interfaces, its inefficient energetics, and sluggish kinetics that are oftentimes significant obstacles for achieving fast charging and high power regimes without compromising battery lifespan. This work propose a Boltzmann-averaged first-principles workflow based on constant potential and constrained density functional theory for estimation of atomic scale factors influencing coupled ion-electron charge transfer kinetics across battery electrode–electrolyte interfaces. The approach estimates diabatic Li + interface energy landscapes as a function of the interface character and operational conditions, needed to simulate charging/discharging currents. Experimental trends for the Li x CoO 2 (0.5 ≤ x ≤ 1.0) electrode in varied organic electrolytes with LiPF 6 and LiClO 4 salts are reproduced, identifying Li + transfer energy and Li + adsorption energy as decisive factors influencing the enhanced kinetics in LiClO 4 -based electrolytes over LiPF 6, rationalized by a stronger surface interaction of ClO 4 –