Investigation of structural fatigue in spinel electrodes using in situ laser probe beam deflection technique

Kyung Yoon Chung, Kwang Bum Kim

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Abstract

The presence of the tetragonal phase at the surface of a LiMn2O4 particle due to a Jahn-Teller effect was previously reported to be one of the reasons for capacity fade observed during cycling of Li//LixMn2O4 in the 4 V range. This study reports on the evidence of the onset of a Jahn-Teller effect above 3 V at the surface of LiMn2O4 particle of thin-film electrodes using in situ laser probe beam deflection technique. The thin film electrode was prepared by electrostatic spray deposition technique. The cyclic deflectograms and cyclic voltammograms were obtained simultaneously, and the potential range responsible for the Jahn-Teller distortion in the 4 V range was determined by differentiating the deflectograms against time. We observed three sets of peaks in both the cathodic and anodic scan of the differential cyclic deflectograms and the magnitudes of these are changed with the scan rate. In the absence of Jahn-Teller distortion, the shape of the differential deflectograms would be identical to that of cyclic voltammograms. Analysis of the differential strain curves obtained from the cyclic deflectograms and the cyclic voltammograms indicates that one of the cathodic peaks of the differential cyclic deflectograms is due to the onset of the Jahn-Teller effect and one of the anodic peaks is due to the relaxation of the tetragonal phase, formed in the previous cathodic scan due to the Jahn-Teller effect, to cubic phase. The Jahn-Teller effect during the cathodic scan is observed to occur around 3.95 ∼ 4.0 V depending on the scan rates, i.e., at slower scan rates the cathodic peak of the differential strain curves became smaller. This could be ascribed to the suppression of the Jahn-Teller effect at near equilibrium conditions.

Original languageEnglish
JournalJournal of the Electrochemical Society
Volume149
Issue number1
DOIs
Publication statusPublished - 2002 Jan 1

Fingerprint

fatigue (materials)
Jahn-Teller effect
spinel
deflection
Fatigue of materials
Electrodes
electrodes
Lasers
probes
lasers
curves
thin films
Thin films
sprayers
spinell
retarding
electrostatics
Electrostatics
cycles

All Science Journal Classification (ASJC) codes

  • Electrochemistry
  • Surfaces, Coatings and Films
  • Surfaces and Interfaces

Cite this

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abstract = "The presence of the tetragonal phase at the surface of a LiMn2O4 particle due to a Jahn-Teller effect was previously reported to be one of the reasons for capacity fade observed during cycling of Li//LixMn2O4 in the 4 V range. This study reports on the evidence of the onset of a Jahn-Teller effect above 3 V at the surface of LiMn2O4 particle of thin-film electrodes using in situ laser probe beam deflection technique. The thin film electrode was prepared by electrostatic spray deposition technique. The cyclic deflectograms and cyclic voltammograms were obtained simultaneously, and the potential range responsible for the Jahn-Teller distortion in the 4 V range was determined by differentiating the deflectograms against time. We observed three sets of peaks in both the cathodic and anodic scan of the differential cyclic deflectograms and the magnitudes of these are changed with the scan rate. In the absence of Jahn-Teller distortion, the shape of the differential deflectograms would be identical to that of cyclic voltammograms. Analysis of the differential strain curves obtained from the cyclic deflectograms and the cyclic voltammograms indicates that one of the cathodic peaks of the differential cyclic deflectograms is due to the onset of the Jahn-Teller effect and one of the anodic peaks is due to the relaxation of the tetragonal phase, formed in the previous cathodic scan due to the Jahn-Teller effect, to cubic phase. The Jahn-Teller effect during the cathodic scan is observed to occur around 3.95 ∼ 4.0 V depending on the scan rates, i.e., at slower scan rates the cathodic peak of the differential strain curves became smaller. This could be ascribed to the suppression of the Jahn-Teller effect at near equilibrium conditions.",
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