Voltage dependent first-principles barriers to Li transport within Li ion battery Solid Electrolyte Interphases (2401.05988v2)

Abstract: Charging a Li ion battery requires Li ion transport between the cathode and the anode. This Li ion transport is dependent upon (among other factors) the electrostatic environment the ion encounters within the Solid Electrolyte Interphase (SEI), which separates the anode from the surrounding electrolyte. Previous first principles work has illuminated the reaction barriers through likely atomistic SEI environments, but has had difficulty accurately reflecting the larger electrostatic potential landscape that an ion encounters moving through the SEI. In this work, we apply the recently developed Quantum Continuum Approximation (QCA) technique to provide an equilibrium electronic potentiostat for first-principles interface calculations. Using QCA, we calculate the potential barrier for Li ion transport through LiF, Li$_2$O, and Li$_2$CO$_3$ SEIs along with LiF-LiF, and LiF-Li$_2$O grain boundaries, all paired with Li metal anodes. We demonstrate that the SEI potential barrier is dependent on the anode electrochemical potentials in each system. Finally, we use these techniques to estimate the change in the diffusion barrier for a Li ion moving in a LiF SEI as a function of anode potential. We find that properly accounting for interface and electronic voltage effects significantly lowers reaction barriers compared to previous literature results.