Determination of the Lamb-Moessbauer factors of LiFePO{sub 4} and FePO{sub 4} for electrochemical in situ and operando measurements in Li-ion batteries

Journal Article · Thu Jan 14 23:00:00 EST 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.10.022· OSTI ID:21372470

Aldon, L ^[1]; Perea, A; Womes, M; Ionica-Bousquet, C M; Jumas, J -C ^[1]

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1. ICGM/AIME (CNRS UMR 5253), Universite Montpellier II, CC 15-02 Place E. Bataillon, 34095 Montpellier Cedex 5 (France)

{sup 57}Fe Moessbauer spectroscopy is a powerful tool to investigate redox reactions during in electrochemical lithium insertion/extraction processes. Electrochemical oxidation of LiFe{sup II}PO{sub 4} (triphylite) in Li-ion batteries results in Fe{sup III}PO{sub 4} (heterosite). LiFePO{sub 4} was synthesized by solid state reaction at 800 deg. C under Ar flow from Li{sub 2}CO{sub 3}, FeC{sub 2}O{sub 4}.2H{sub 2}O and NH{sub 4}H{sub 2}PO{sub 4} precursors in stoichiometric composition. FePO{sub 4} was prepared from chemical oxidation of LiFePO{sub 4} using bromine as oxidative agent. For both materials a complete {sup 57}Fe Moessbauer study as a function of the temperature has been carried out. The Debye temperatures are found to be theta{sub M}=336 K for LiFePO{sub 4} and theta{sub M}=359 K for FePO{sub 4}, leading to Lamb-Moessbauer factors f{sub 300K}=0.73 and 0.77, respectively. These data will be useful for a precise estimation of the relative amounts of each species in a mixture. - Graphical abstract: Relative amount of FePO{sub 4} obtained by Moessbauer and electrochemical data. We have corrected Moessbauer spectral intensities with our f factor of both LiFePO{sub 4} and FePO{sub 4}. Open (filled) squares correspond to values obtained during charging (discharging) process. The dashed line, given as a guideline for the eye, corresponds to the ideal case were amounts deduced from different experimental measurements are equal.

• OSTI ID: 21372470
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 1 Vol. 183; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ALKALI METAL COMPOUNDS
AMMONIUM COMPOUNDS
AMMONIUM PHOSPHATES
CARBON COMPOUNDS
CARBONATES
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
DEBYE TEMPERATURE
ELECTRIC BATTERIES
ELECTROCHEMICAL CELLS
ELECTROCHEMISTRY
ENERGY STORAGE SYSTEMS
ENERGY SYSTEMS
IONS
IRON COMPOUNDS
IRON PHOSPHATES
LITHIUM CARBONATES
LITHIUM COMPOUNDS
LITHIUM IONS
LITHIUM PHOSPHATES
MINERALS
MOESSBAUER EFFECT
OLIVINE
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS
REDOX REACTIONS
SILICATE MINERALS
STOICHIOMETRY
TEMPERATURE RANGE
TEMPERATURE RANGE 0273-0400 K
TEMPERATURE RANGE 1000-4000 K
TRANSITION ELEMENT COMPOUNDS