NDLI: Operando57Fe Mössbauer and XRD investigation of LixMnyFe1−yPO4/C composites (y = 0; 0.25)

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Back cover

RSC Advances Vol - 2 Issue - 4

RSC Advances Vol -1

RSC Advances Vol -0

Operando⁵⁷Fe Mössbauer and XRD investigation of Li_xMn_yFe_1−yPO₄/C composites (y = 0; 0.25)

Content Provider	Royal Society of Chemistry (RSC)
Author	Sougrati, Moulay T. Jumas, Jean-Claude Tessier, Cécile Fraisse, Bernard Perea, Alexis Ionica-Bousquet, Costana M. Aldon, Laurent
Copyright Year	2012
Abstract	LiMn0.25Fe0.75PO4 and LiFePO4 powders have been synthesized by a ceramic route. A comparative investigation of their electrochemical behaviour using operando57Fe Mössbauer and X-ray diffraction is reported. The partial substitution of Fe by Mn atoms enhances the energy density of the olivine phase since the average potential of cycling is increased. The complementarity of the operando techniques used in this study allows the monitoring of changes in the local electronic environment and the lattice modifications that are directly linked to the redox reaction mechanisms. The lithium deintercalation/intercalation mechanism in LiMn0.25Fe0.75PO4 has been found to be completely different from LiFePO4. During the charge, the LiMn0.25Fe0.75PO4 phase has been found to undergo three well defined and reversible reactions; (i) a biphasic reaction at 3.46 V corresponding to a partial oxidation of FeII into FeIII, (ii) the remaining FeII is oxidized in a monophasic reaction between 3.46 and 4.1 V. Finally, (iii) MnII is converted to MnIII by mean of biphasic reaction at 4.2 V. Interestingly, the FeIII Mössbauer signature has been found to be sensitive to the oxidation of MnII since this oxidation is accompanied with a significant increase in the quadrupole splitting. The non-optimized LiMn0.25Fe0.75PO4electrode has been successfully cycled with constant capacity (120 mAh.g−1) for more than 40 cycles at room temperature.
Starting Page	2080
Ending Page	2086
Page Count	7
File Format	HTM / HTML PDF
ISSN	20462069
Volume Number	2
Issue Number	5
Journal	RSC Advances
DOI	10.1039/c1ra00256b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	X-ray crystallography Olivine Quadrupole splitting Electrochemistry Redox Energy density Lithium Crystal structure
Content Type	Text
Resource Type	Article
Subject	Chemistry Chemical Engineering

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