Charge Transfer Kinetics at the Solid-Solid Interface in Porous Electrodes
arXiv:1404.0859 · doi:10.1038/ncomms4585
Abstract
Interfacial charge transfer is widely assumed to obey Butler-Volmer kinetics. For certain liquid-solid interfaces, Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report a simple method to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures. The fitted reorganization energy matches the Born solvation energy for electron transfer from carbon to the iron redox site. The kinetics are thus limited by electron transfer at the solid-solid (carbon-LixFePO4) interface, rather than by ion transfer at the liquid-solid interface, as previously assumed. The proposed experimental method generalizes Chidsey's method for phase-transforming particles and porous electrodes, and the results show the need to incorporate Marcus kinetics in modeling batteries and other electrochemical systems.
13 pages, 5 figures
References in corpus (5)
- Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics
- Suppression of Phase Separation in LiFePO4 Nanoparticles During Battery Discharge
- Coherency strain and the kinetics of phase separation in LiFePO4
- Theory of Nucleation in Phase-separating Nanoparticles
- Statistical Kinetics of Phase-Transforming Nanoparticles in LiFePO4 Porous Electrodes
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