Journal article
In Situ Studies of Fe4+ Stability in β-Li3Fe2(PO4)3 Cathodes for Li Ion Batteries
Department of Energy Conversion and Storage, Technical University of Denmark1
Atomic Scale Materials Modelling, Department of Energy Conversion and Storage, Technical University of Denmark2
Department of Physics, Technical University of Denmark3
Neutrons and X-rays for Materials Physics, Department of Physics, Technical University of Denmark4
Applied Electrochemistry, Department of Energy Conversion and Storage, Technical University of Denmark5
Fundamental Electrochemistry, Department of Energy Conversion and Storage, Technical University of Denmark6
In commercial Fe-based batteries the Fe2+/Fe3+ oxidation states are used, however by also utilizing the Fe4+ oxidation state, intercalation of up to two Li ions per Fe ion could be possible. In this study, we investigate whether Fe4+ can be formed and stabilized in β-Li3Fe2(PO4)3. The work includes in situ synchrotron X-ray powder diffraction studies (XRPD) during charging of β-Li3Fe2(PO4)3 up to 5.0 V vs.
Li/Li+. A novel capillary-based micro battery cell for in situ XRPD has been designed for this. During charge, a plateau at 4.5 V was found and a small contraction in volume was observed, indicating some Li ion extraction. The volume change of the rhombohedral unit cell is anisotropic, with a decrease in the a parameter and an increase in the c parameter during the Li ion extraction.
Unfortunately, no increased discharge capacity was observed and Mössbauer spectroscopy showed no evidence of Fe4+ formation. Oxidation of the organic electrolyte is inevitable at 4.5 V but this alone cannot explain the volume change. Instead, a reversible oxygen redox process (O2− → O−) could possibly explain and charge compensate for the reversible extraction of lithium ions from β-Li3Fe2(PO4)3.
Language: | English |
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Publisher: | The Electrochemical Society |
Year: | 2015 |
Pages: | 20A531-A537 |
ISSN: | 00134651 and 19457111 |
Types: | Journal article |
DOI: | 10.1149/2.0141504jes |
ORCIDs: | Johnsen, Rune E. , Norby, Poul , Frandsen, Cathrine , Kammer Hansen, Kent and Holtappels, Peter |