期刊
ELECTROCHIMICA ACTA
卷 111, 期 -, 页码 474-490出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.electacta.2013.08.014
关键词
Cahn-Hilliard-reaction; LiFePO4; Two-scale; Phase-field; Shrinking-core
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. (C) 2013 Elsevier Ltd. All rights reserved.
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