Nonequilibrium Thermodynamics of Porous Electrodes

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 p...

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Bibliographic Details
Published inarXiv.org
Main Authors Ferguson, Todd R, Bazant, Martin Z
Format Paper
LanguageEnglish
Published Ithaca Cornell University Library, arXiv.org 23.08.2012
Subjects
Charge transfer
Electric potential
Electrodes
Fluxes
Lithium-ion batteries
Low currents
Nonequilibrium thermodynamics
Phase separation
Phase transitions
Porosity
Reaction kinetics
Thermodynamic equilibrium
Tortuosity
Variation
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Summary: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.
ISSN:2331-8422