Solvent Diffusion Model for Aging of Lithium-Ion Battery Cells

This work presents a rigorous continuum mechanics model of solvent diffusion describing the growth of solid-electrolyte interfaces (SEIs) in Li-ion cells incorporating carbon anodes. The model assumes that a reactive solvent component diffuses through the SEI and undergoes two-electron reduction at the carbon-SEI interface. Solvent reduction produces an insoluble product, resulting in increasing SEI thickness. The model predicts that the SEI thickness increases linearly with the square root of time. Experimental data from the literature for capacity loss in two types of prototype Li-ion cells validates the solvent diffusion model. We use the model to estimate SEI thickness and extract solvent diffusivity values from the capacity loss data. Solvent diffusivity values have an Arrhenius temperature dependence consistent with solvent diffusion through a solid SEI. The magnitudes of the diffusivities and activation energies are comparable to literature values for hydrocarbon diffusion in carbon molecular sieves and zeolites. These findings, viewed in the context of recent SEI morphology studies, suggest that the SEI may be viewed as a single layer with both micro- and macroporosity that controls the ingress of electrolyte, anode passivation by the SEI, and cell performance during initial cycling as well as long-term operation. © 2004 The Electrochemical Society. All rights reserved.