Effect of temperature on the kinetics and thermodynamics of electrochemical insertion of Li-ions into a graphite electrode

M. D. Levi, C. Wang, D. Aurbach, Z. Chvoj

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38 Scopus citations


We report on the potential and temperature dependences of the differential intercalation capacitance, Cdif, and the chemical diffusion coefficient, D, during Li intercalation into a graphite anode by a combined application of slow-scan rate cyclic voltammetry (SSCV) and the potentiostatic intermittent titration technique (PITT). Drastically different behavior was observed within the short-time ranges of the PITT response measured for a two-phase coexistence domain and a solid solution of phases 4 and 3. Electroanalytical evidence for small droplet formation (nucleation) of a new phase in the bulk of the old one was found for the former domain, showing good correlation with in situ XRD studies. SSCV data obtained in the 25-80 °C temperature range were in excellent agreement with the published temperature-concentration phase diagrams built on the basis of detailed XRD characterizations. The simultaneous appearance of maxima on Cdif versus E plots and minima on the related log D versus E plots in the two-phase domains was rationalized in terms of a lattice gas model with single site energy, and highly attractive interactions between the intercalated guest atoms. The electroanalytical behavior of graphite within the solid-solution domain (a mixture of phases 4 and 3) was interpreted semi-quantitatively on the basis of a model that took into account the presence of two sub-lattices of different energy (a model of "energetic heterogeneity") for Li accommodation, and attractive interactions between the guest atoms on each sub-lattice, or, alternatively, due to in-plane order-disorder transitions because of short-range repulsive interactions between the intercalated guest species.

Original languageEnglish
Pages (from-to)187-203
Number of pages17
JournalJournal of Electroanalytical Chemistry
Issue number2
StatePublished - 1 Feb 2004

Bibliographical note

Funding Information:
This work has been supported by the Grant Agency of Academy of Sciences of the Czech Republic, N IAA 1010207. We are grateful to Dr. E. Vakarin for helpful discussions of the results related to application of surface heterogeneity model to Li intercalation in the solid-solution domain of Li x C 6 .


  • Diffusion coefficient
  • Elevated temperatures
  • First-order phase transition
  • Lattice gas model
  • Li-ion cell
  • LiC
  • PITT


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