Nonequilibrium Thermodynamics of Porous Electrodes

TL;DR

This paper develops a thermodynamic framework for porous electrodes in batteries, incorporating phase transformations and non-ideal effects, and demonstrates its ability to predict complex behaviors like phase separation and voltage fluctuations.

Contribution

It extends porous electrode theory to include non-ideal active materials and phase transformations using non-equilibrium thermodynamics, providing new insights into electrode dynamics.

Findings

Predicts phase separation and voltage fluctuations in porous electrodes.

Shows the influence of transport limitations and kinetics on battery performance.

Validates model predictions with experimental observations of mosaic instabilities.

Abstract

We reformulate and extend porous electrode theory for non-ideal active materials, including those capable of phase transformations. Using principles of non-equilibrium thermodynamics, we relate the cell voltage, ionic fluxes, and Faradaic charge-transfer kinetics to the variational electrochemical potentials of ions and electrons. The Butler-Volmer exchange current is consistently expressed in terms of the activities of the reduced, oxidized and transition states, and the activation overpotential is defined relative to the local Nernst potential. We also apply mathematical bounds on effective diffusivity to estimate porosity and tortuosity corrections. The theory is illustrated for a Li-ion battery with active solid particles described by a Cahn-Hilliard phase-field model. Depending on the applied current and porous electrode properties, the dynamics can be limited by electrolyte transport, solid diffusion and phase separation, or intercalation kinetics. In phase-separating porous electrodes, the model predicts narrow reaction fronts, mosaic instabilities and voltage fluctuations at low current, consistent with recent experiments, which could not be described by existing porous electrode models.