Phase-field study of electrochemical reactions at exterior and interior interfaces in Li-Ion battery electrode particles

TL;DR

This study develops a comprehensive phase-field model to simulate electrochemical reactions, fracture, and phase segregation in Li-ion battery particles, revealing how reaction timescales and diffusivity anisotropy influence material behavior and crack propagation.

Contribution

The paper introduces a novel 3D phase-field model incorporating fracture, anisotropic diffusion, and electrochemical reactions for Li-ion battery particles, including crack surface reactions.

Findings

Reaction timescale affects phase segregation and diffusion behavior.

Lithium concentration gradients increase reaction rates at phase interfaces.

Crack propagation is driven by phase segregation during delithiation.

Abstract

To study the electrochemical reaction on surfaces, phase interfaces, and crack surfaces in the lithium ion battery electrode particles, a phase-field model is developed, which describes fracture in large strains and anisotropic Cahn-Hilliard-Reaction. Thereby the concentration-dependency of the elastic properties and the anisotropy of diffusivity are also considered. The implementation in 3D is carried out by isogeometric finite element methods in order to treat the high order terms in a straightforward sense. The electrochemical reaction is modeled through a modified Butler-Volmer equation to account for the influence of the phase change on the reaction on exterior surfaces. The reaction on the crack surfaces is considered through a volume source term weighted by a term related to the fracture order parameter. Based on the model, three characteristic examples are considered to reveal the electrochemical reactions on particle surfaces, phase interfaces, and crack surfaces, as well as their influence on the particle material behavior. Results show that the ratio between the timescale of reaction and the diffusion can have a significant influence on phase segregation behavior, as well as the anisotropy of diffusivity. In turn, the distribution of the lithium concentration greatly influences the reaction on the surface, especially when the phase interfaces appear on exterior surfaces or crack surfaces. The reaction rate increases considerably at phase interfaces, due to the large lithium concentration gradient. Moreover, simulations demonstrate that the segregation of a Li-rich and a Li-poor phase during delithiation can drive the cracks to propagate. Results indicate that the model can capture the electrochemical reaction on the freshly cracked surfaces.