Structural assessment of the electrochemical performance of LixCoO2 membrane electrodes by X-ray diffraction and absorption refinements |
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Authors: | J M Rosolen P Ballirano M Berrettoni F Decker M Gregorkiewitz |
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Institution: | (1) Dip. di Scienze Chimiche, Universita di Roma, P.le A. Moro 5, I-00185 Roma, Italy;(2) Dip. di Scienze della Terra, Universita di Roma, P.le A. Moro 5, I-00185 Roma, Italy;(3) Dip. Matematica e Fisica, Universita di Camerino, I-62032 Camerino, Italy;(4) Dep. de Quimica-Ribeirao, Universidade de Sao Paulo-FFCLRP, 14040-901 Preto, Brazil;(5) Present address: Dip. di Scienze della Terra, Universita di Siena, v. della Cerchia 3, 1-53100 Siena, Italy |
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Abstract: | LixCoO2 samples with different nominal load x were prepared submitting HT-LiCoO2 membrane electrodes to electrochemical polarisation, followed by aging in open circuit conditions. Care was taken to obtain
samples for both positive and negative overcharge beyond the canonical regime (0.6≤x≤1) of the LixCoO2 electrode. For 11 samples in the range 0.37≤x≤1.43, Rietveld refinements of X-ray diffraction data were performed, with Li
at 3a, Co at 3b and O at 6c in the space group R-3m as starting model. In the range 0.37≤x≤1, results show a continuous variation
of theac unit cell and structural parameters such as the lithium site occupancy and the Li-O and Co-O interatomic distances. For samples
in the range 1≤x≤1.43, Li2CO3 was detected as an impurity which might be due to decomposition of the electrolyte, and, if the negative overcharge was high
enough, an abnormally high electron density at the 3a site indicates some Li→Co substitution. Results from Co-K edge X-ray
absorption spectroscopy for the samples with x=0.37, 0.89, 1 and 1.43 show a clear shift of the absorption maximum with the
oxidation state of Co and support the conclusions from Rietveld refinement. GNXAS refinement of EXAFS spectra for the samples
with x=0.37 and 1 suggest that cation disordering may occur also for deep lithium deintercalation (positive overcharge), a
fact which was not detectable from diffraction data. |
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