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Title: Solid-state electrochemical kinetics of Li-ion intercalation into Li{sub 1{minus}x}CoO{sub 2}: Simultaneous application of electroanalytical techniques SSCV, PITT, and EIS

Abstract

The electroanalytical behavior of thin Li{sub 1{minus}x}CoO{sub 2} electrodes is elucidated by the simultaneous application of three electroanalytical techniques: slow-scan-rate cyclic voltammetry (SSCV), potentiostatic intermittent titration technique, and electrochemical impedance spectroscopy. The data were treated within the framework of a simple model expressed by a Frumkin-type sorption isotherm. The experimental SSCV curves were well described by an equation combining such an isotherm with the Butler-Volmer equation for slow interfacial Li-ion transfer. The apparent attraction constant was {minus}4.2, which is characteristic of a quasi-equilibrium, first-order phase transition. Impedance spectra reflected a process with the following steps: Li{sup +} ion migration in solution, Li{sup +} ion migration through surface films, strongly potential-dependent charge-transfer resistance, solid-state Li{sup +} diffusion, and accumulation of the intercalants into the host materials. An excellent fit was found between these spectra and an equivalent circuit, including a Voigt-type analog (Li{sup +} migration through multilayer surface films and charge transfer) in series with a finite-length Warburg-type element (Li{sup +} solid-state diffusion), and a capacitor (Li accumulation). In this paper, the authors compare the solid-state diffusion time constants and the differential intercalation capacities obtained by the three electroanalytical techniques.

Authors:
; ; ; ;  [1]; ;  [2]
  1. Bar-Ilan Univ., Ramat-Gan (Israel). Dept. of Chemistry
  2. Merck KGaA, Darmstadt (Germany)
Publication Date:
OSTI Identifier:
345313
Resource Type:
Journal Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 146; Journal Issue: 4; Other Information: PBD: Apr 1999
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; METAL-NONMETAL BATTERIES; LITHIUM; CLATHRATES; LITHIUM OXIDES; COBALT OXIDES; ELECTROCHEMISTRY; CHEMICAL REACTION KINETICS; MATHEMATICAL MODELS; MEASURING METHODS

Citation Formats

Levi, M D, Salitra, G, Markovsky, B, Teller, H, Aurbach, D, Heider, U, and Heider, L. Solid-state electrochemical kinetics of Li-ion intercalation into Li{sub 1{minus}x}CoO{sub 2}: Simultaneous application of electroanalytical techniques SSCV, PITT, and EIS. United States: N. p., 1999. Web. doi:10.1149/1.1391759.
Levi, M D, Salitra, G, Markovsky, B, Teller, H, Aurbach, D, Heider, U, & Heider, L. Solid-state electrochemical kinetics of Li-ion intercalation into Li{sub 1{minus}x}CoO{sub 2}: Simultaneous application of electroanalytical techniques SSCV, PITT, and EIS. United States. https://doi.org/10.1149/1.1391759
Levi, M D, Salitra, G, Markovsky, B, Teller, H, Aurbach, D, Heider, U, and Heider, L. Thu . "Solid-state electrochemical kinetics of Li-ion intercalation into Li{sub 1{minus}x}CoO{sub 2}: Simultaneous application of electroanalytical techniques SSCV, PITT, and EIS". United States. https://doi.org/10.1149/1.1391759.
@article{osti_345313,
title = {Solid-state electrochemical kinetics of Li-ion intercalation into Li{sub 1{minus}x}CoO{sub 2}: Simultaneous application of electroanalytical techniques SSCV, PITT, and EIS},
author = {Levi, M D and Salitra, G and Markovsky, B and Teller, H and Aurbach, D and Heider, U and Heider, L},
abstractNote = {The electroanalytical behavior of thin Li{sub 1{minus}x}CoO{sub 2} electrodes is elucidated by the simultaneous application of three electroanalytical techniques: slow-scan-rate cyclic voltammetry (SSCV), potentiostatic intermittent titration technique, and electrochemical impedance spectroscopy. The data were treated within the framework of a simple model expressed by a Frumkin-type sorption isotherm. The experimental SSCV curves were well described by an equation combining such an isotherm with the Butler-Volmer equation for slow interfacial Li-ion transfer. The apparent attraction constant was {minus}4.2, which is characteristic of a quasi-equilibrium, first-order phase transition. Impedance spectra reflected a process with the following steps: Li{sup +} ion migration in solution, Li{sup +} ion migration through surface films, strongly potential-dependent charge-transfer resistance, solid-state Li{sup +} diffusion, and accumulation of the intercalants into the host materials. An excellent fit was found between these spectra and an equivalent circuit, including a Voigt-type analog (Li{sup +} migration through multilayer surface films and charge transfer) in series with a finite-length Warburg-type element (Li{sup +} solid-state diffusion), and a capacitor (Li accumulation). In this paper, the authors compare the solid-state diffusion time constants and the differential intercalation capacities obtained by the three electroanalytical techniques.},
doi = {10.1149/1.1391759},
url = {https://www.osti.gov/biblio/345313}, journal = {Journal of the Electrochemical Society},
number = 4,
volume = 146,
place = {United States},
year = {1999},
month = {4}
}