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 · Fri Jan 15 00:00:00 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]

---

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, Vol. 183, Issue 1; Other Information: DOI: 10.1016/j.jssc.2009.10.022; PII: S0022-4596(09)00506-4; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

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