The application of electroanalytical methods to the analysis of phase transitions during intercalation of ions into electrodes |
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Authors: | M D Levi D Aurbach |
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Institution: | (1) Department of Chemistry, Bar-Ilan University, Ramat Gan, 52900, Israel |
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Abstract: | Mechanisms of first-order phase transition induced by electrochemical intercalation of Li ions into composite graphite electrode
are studied both theoretically, in the framework of lattice gas models, and experimentally, by a combination of electroanalytical
techniques, such as cyclic voltammetry, potentiostatic intermittent titration (PITT), galvanostatic intermittent titration
(GITT), and electrochemical impedance spectroscopy (EIS). From the analysis of the mismatch between the accessible phase-transition
rate constants and the characteristic time windows for various electroanalytical methods, we conclude that only a combined
application of these techniques provides sufficient, self-consistent information on the mechanisms of phase transitions in
graphite electrodes. The advantages and disadvantages in using these techniques are discussed. PITT with a small potential
step is the most appropriate tool for measuring the entire sequence of rate-determining steps of phase transitions as a function
of time. The latter technique can be conveniently used for quantitative analysis of slow nucleation and the growth of new
phases in the bulk of the old one, followed by the coalescence of nuclei and the formation of phase boundaries between the
coexisting phases. The movement of this boundary into the electrode’s bulk has been properly modeled in terms of two alternative
models.
“Contribution to the International Workshop on Electrochemistry of Electroactive Materials (WEEM-2006), Repino, Russia, 24–29
June 2006.” |
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Keywords: | PITT GITT EIS Li-ion batteries Intercalation Nucleation and growth Diffusion Differential intercalation capacitance Chemical diffusion coefficient |
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