A mathematical model for mechanically-induced deterioration of the binder in lithium-ion electrodes

TL;DR

This paper develops a multiscale mathematical model to understand how mechanical deformations from electrolyte absorption and cycling cause binder deterioration in lithium-ion battery electrodes, validated by microscopy images.

Contribution

It introduces a novel two-dimensional poroviscoelastic model capturing microstructure effects and distinguishes deformation patterns caused by different mechanical forces.

Findings

Swelling induces binder delamination parallel to the current collector.

Cycling causes orthogonal binder delamination.

Model predictions qualitatively match microscopy images.

Abstract

This study is concerned with modeling detrimental deformations of the binder phase within lithium-ion batteries that occur during cell assembly and usage. A two-dimensional poroviscoelastic model for the mechanical behavior of porous electrodes is formulated and posed on a geometry corresponding to a thin rectangular electrode, with a regular square array of microscopic circular electrode particles, stuck to a rigid base formed by the current collector. Deformation is forced both by (i) electrolyte absorption driven binder swelling, and; (ii) cyclic growth and shrinkage of electrode particles as the battery is charged and discharged. The governing equations are upscaled in order to obtain macroscopic effective-medium equations. A solution to these equations is obtained, in the asymptotic limit that the height of the rectangular electrode is much smaller than its width, that shows the macroscopic deformation is one-dimensional. The confinement of macroscopic deformations to one dimension is used to obtain boundary conditions on the microscopic problem for the deformations in a 'unit cell' centered on a single electrode particle. The resulting microscale problem is solved using numerical (finite element) techniques. The two different forcing mechanisms are found to cause distinctly different patterns of deformation within the microstructure. Swelling of the binder induces stresses that tend to lead to binder delamination from the electrode particle surfaces in a direction parallel to the current collector, whilst cycling causes stresses that tend to lead to delamination orthogonal to that caused by swelling. The differences between the cycling-induced damage in both: (i) anodes and cathodes, and; (ii) fast and slow cycling are discussed. Finally, the model predictions are compared to microscopy images of nickel manganese cobalt oxide cathodes and a qualitative agreement is found.