Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
186651 | Electrochimica Acta | 2013 | 17 Pages |
We construct a two-scale mathematical model for modern, high-rate LiFePO4 cathodes. We attempt to validate against experimental data using two forms of the phase-field model developed recently to represent the concentration of Li+ in nano-sized LiFePO4 crystals. We also compare this with the shrinking-core based model we developed previously. Validating against high-rate experimental data, in which electronic and electrolytic resistances have been reduced is an excellent test of the validity of the crystal-scale model used to represent the phase-change that may occur in LiFePO4 material. We obtain poor fits with the shrinking-core based model, even with fitting based on “effective” parameter values. Surprisingly, using the more sophisticated phase-field models on the crystal-scale results in poorer fits, though a significant parameter regime could not be investigated due to numerical difficulties. Separate to the fits obtained, using phase-field based models embedded in a two-scale cathodic model results in “many-particle” effects consistent with those reported recently.