• DOI:10.1137/130937548
• Corpus ID: 1804660

Phase Separation Dynamics in Isotropic Ion-Intercalation Particles

@article{Zeng2014PhaseSD,
  title={Phase Separation Dynamics in Isotropic Ion-Intercalation Particles},
  author={Yi Zeng and Martin Z. Bazant},
  journal={SIAM J. Appl. Math.},
  year={2014},
  volume={74},
  pages={980-1004}
}

• Yi Zeng, M. Bazant
• Published 18 September 2013
• Physics, Materials Science
• SIAM J. Appl. Math.

Lithium-ion batteries exhibit complex nonlinear dynamics, resulting from diffusion and phase transformations coupled to ion intercalation reactions. Using the recently developed Cahn-Hilliard reaction (CHR) theory, we investigate a simple mathematical model of ion intercalation in a spherical solid nanoparticle, which predicts transitions from solid-solution radial diffusion to two-phase shrinking-core dynamics. This general approach extends previous Li-ion battery models, which either neglect phase separation or postulate a spherical shrinking-core phase boundary, by predicting phase separation only under appropriate circumstances. The effect of the applied current is captured by generalized Butler-Volmer kinetics, formulated in terms of diffusional chemical potentials, and the model consistently links the evolving concentration profile to the battery voltage. We examine sources of charge/discharge asymmetry, such as asymmetric charge transfer and surface "wetting" by ions within the solid, which can lead to three distinct phase regions. In order to solve the fourth-order nonlinear CHR initial-boundary-value problem, a control-volume discretization is developed in spherical coordinates. The basic physics are illustrated by simulating many representative cases, including a simple model of the popular cathode material, lithium iron phosphate (neglecting crystal anisotropy and coherency strain). Analytical approximations are also derived for the voltage plateau as a function of the applied current.