TY - JOUR
T1 - The application of electroanalytical methods to the analysis of phase transitions during intercalation of ions into electrodes
AU - Levi, M. D.
AU - Aurbach, D.
PY - 2007/8
Y1 - 2007/8
N2 - 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.
AB - 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.
KW - Chemical diffusion coefficient
KW - Differential intercalation capacitance
KW - Diffusion
KW - EIS
KW - GITT
KW - Intercalation
KW - Li-ion batteries
KW - Nucleation and growth
KW - PITT
UR - http://www.scopus.com/inward/record.url?scp=34248350801&partnerID=8YFLogxK
U2 - 10.1007/s10008-007-0264-x
DO - 10.1007/s10008-007-0264-x
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AN - SCOPUS:34248350801
SN - 1432-8488
VL - 11
SP - 1031
EP - 1042
JO - Journal of Solid State Electrochemistry
JF - Journal of Solid State Electrochemistry
IS - 8
ER -