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Surface analysis of LiMn2O4 electrodes in carbonate based electrolytes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
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2002 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, Vol. 149, no 1, A69-A78 p.Article in journal (Refereed) Published
Abstract [en]

The interface chemistry of LixMn2O4 electrodes in carbonate-based electrolytes has been investigated using X-ray photoelectron spectroscopy, infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy following cycling or storage in ⟨LiMn2O4| ethylene carbonate/dimethyl carbonate LiPF6/LiBF4|Li⟩ cells. No significant changes were found in the elemental composition of surface films formed on cycled and stored samples, suggesting that surface-film formation is not governed by processes associated with cell cycling. The amount of surface species increases with storage time and cycle number at ambient temperature, where LiF, LixPFyOz products and some polyether-type polymeric compound could be identified as reaction products on the cathode surface. A lithium-rich manganese oxide layer develops on the surface of the cathode particles under continued storage and cycling. The thickness of the surface layer decreases rather than increases with storage at a higher state-of-charge. More carbon compounds are preserved on the electrode surface using LiBF4 rather than LiPF6 as electrolyte salt.

Place, publisher, year, edition, pages
2002. Vol. 149, no 1, A69-A78 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-89455DOI: 10.1149/1.1426398OAI: oai:DiVA.org:uu-89455DiVA: diva2:160902
Available from: 2001-10-03 Created: 2001-10-03 Last updated: 2013-06-20Bibliographically approved
In thesis
1. LiMn2O4 as a Li-ion Battery Cathode. From Bulk to Electrolyte Interface
Open this publication in new window or tab >>LiMn2O4 as a Li-ion Battery Cathode. From Bulk to Electrolyte Interface
2001 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

LiMn2O4 is ideal as a high-capacity Li-ion battery cathode material by virtue of its low toxicity, low cost, and the high natural abundance of Mn. Surface related reactions and bulk kinetics have been the major focus of this work. The main techniques exploited have been: electrochemical cycling, X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy and thermal analysis.

Interface formation between the LiMn2O4 cathode and carbonate-based electrolytes has been followed under different pre-treatment conditions. The variables have been: number of charge/discharge cycles, storage time, potential, electrolyte salt and temperature. The formation of the surface layer was found not to be governed by electrochemical cycling. The species precipitating on the surface of the cathodes at ambient temperature have been determined to comprise a mixture of organic and inorganic compounds: LiF, LixPFy (or LixBFy, depending on the electrolyte salt used), LixPOyFz (or LixBOyFz) and poly(oxyethylene). Additional compounds were found at elevated temperatures: phosphorous oxides (or boron oxides) and polycarbonates. A model has been presented for the formation of these surface species at elevated temperatures.

The cathode surface structure was found to change towards a lithium-rich and Mn3+-rich compound under self-discharge. The reduction of LiMn2O4, in addition to the high operating potential, induces oxidation of the electrolyte at the cathode surface.

A novel in situ electrochemical/structural set-up has facilitated a study of the kinetics in the LiMn2O4 electrode. The results eliminate solid-phase diffusion as the rate-limiting factor in electrochemical cycling. The electrode preparation method used results in good utilisation of the electrode, even at high discharge rates.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2001. 53 p.
Series
Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1104-232X ; 651
Keyword
Chemistry, cathode materials, lithium manganese oxide, interface, surface layer, electrode kinetics, Kemi
National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-1397 (URN)91-554-5100-4 (ISBN)
Public defence
2001-09-21, Häggsalen, Ångströmlaboratoriet, Uppsala, Uppsala, 10:15
Opponent
Available from: 2001-10-03 Created: 2001-10-03Bibliographically approved

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Gustafsson, Torbjörn

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