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Title: Moessbauer spectra as a 'fingerprint' in tin-lithium compounds: Applications to Li-ion batteries

Abstract

Several Li-Sn crystalline phases, i.e. Li{sub 2}Sn{sub 5}, LiSn, Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2} and Li{sub 22}Sn{sub 5} were prepared by ball-milling and characterized by X-ray powder diffraction and {sup 119}Sn Moessbauer spectroscopy. The analysis of the Moessbauer hyperfine parameters, i.e. isomer shift ({delta}) and quadrupole splitting ({delta}), made it possible to define two types of Li-Sn compounds: the Sn-richest compounds (Li{sub 2}Sn{sub 5}, LiSn) and the Li-richest compounds (Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2}, Li{sub 22}Sn{sub 5}). The isomer shift values ranged from 2.56 to 2.38 mm s{sup -1} for Li{sub 2}Sn{sub 5}, LiSn and from 2.07 to 1.83 mm s{sup -1} for Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2} and Li{sub 22}Sn{sub 5}, respectively. A {delta}-{delta} correlation diagram is introduced in order to identify the different phases observed during the electrochemical process of new Sn-based materials. This approach is illustrated by the identification of the phases obtained at the end of the first discharge of {eta}-Cu{sub 6}Sn{sub 5} and SnB{sub 0.6}P{sub 0.4}O{sub 2.9}. - Graphical abstract: {delta}-{delta} correlation diagram for the different tin sites of the Li-Sn compounds. The symbolsmore » denote the different Li-Sn phases and the products obtained at the end of the discharge of {eta}-Cu{sub 6}Sn{sub 5} and SnB{sub 0.6}P{sub 0.4}O{sub 2.9}. The grey and the light-grey areas show Sn-centred polyhedra without and with one Sn first-nearest neighbours, respectively.« less

Authors:
 [1];  [2];  [2];  [2];  [3];  [3];  [3]
  1. Laboratoire des Agregats Moleculaires et Materiaux Inorganiques (UMR 5072 CNRS), CC15, Universite Montpellier II, Place Eugene Bataillon, 34095 Montpellier Cedex 5 (France), E-mail: frobert@univ-montp2.fr
  2. Laboratoire des Agregats Moleculaires et Materiaux Inorganiques (UMR 5072 CNRS), CC15, Universite Montpellier II, Place Eugene Bataillon, 34095 Montpellier Cedex 5 (France)
  3. Laboratoire de Reactivite et Chimie des Solides (UMR 6007 CNRS), Universite de Picardie Jules Verne, 33 rue Saint Leu, 80039 Amiens (France)
Publication Date:
OSTI Identifier:
21015656
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2006.10.026; PII: S0022-4596(06)00566-4; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DIAGRAMS; ELECTROCHEMISTRY; ISOMER SHIFT; LITHIUM ALLOYS; LITHIUM COMPOUNDS; LITHIUM IONS; MOESSBAUER EFFECT; TIN ALLOYS; TIN COMPOUNDS; X-RAY DIFFRACTION

Citation Formats

Robert, F., Lippens, P.E., Olivier-Fourcade, J., Jumas, J.-C., Gillot, F., Morcrette, M., and Tarascon, J.-M. Moessbauer spectra as a 'fingerprint' in tin-lithium compounds: Applications to Li-ion batteries. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.10.026.
Robert, F., Lippens, P.E., Olivier-Fourcade, J., Jumas, J.-C., Gillot, F., Morcrette, M., & Tarascon, J.-M. Moessbauer spectra as a 'fingerprint' in tin-lithium compounds: Applications to Li-ion batteries. United States. doi:10.1016/j.jssc.2006.10.026.
Robert, F., Lippens, P.E., Olivier-Fourcade, J., Jumas, J.-C., Gillot, F., Morcrette, M., and Tarascon, J.-M. Mon . "Moessbauer spectra as a 'fingerprint' in tin-lithium compounds: Applications to Li-ion batteries". United States. doi:10.1016/j.jssc.2006.10.026.
@article{osti_21015656,
title = {Moessbauer spectra as a 'fingerprint' in tin-lithium compounds: Applications to Li-ion batteries},
author = {Robert, F. and Lippens, P.E. and Olivier-Fourcade, J. and Jumas, J.-C. and Gillot, F. and Morcrette, M. and Tarascon, J.-M.},
abstractNote = {Several Li-Sn crystalline phases, i.e. Li{sub 2}Sn{sub 5}, LiSn, Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2} and Li{sub 22}Sn{sub 5} were prepared by ball-milling and characterized by X-ray powder diffraction and {sup 119}Sn Moessbauer spectroscopy. The analysis of the Moessbauer hyperfine parameters, i.e. isomer shift ({delta}) and quadrupole splitting ({delta}), made it possible to define two types of Li-Sn compounds: the Sn-richest compounds (Li{sub 2}Sn{sub 5}, LiSn) and the Li-richest compounds (Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2}, Li{sub 22}Sn{sub 5}). The isomer shift values ranged from 2.56 to 2.38 mm s{sup -1} for Li{sub 2}Sn{sub 5}, LiSn and from 2.07 to 1.83 mm s{sup -1} for Li{sub 7}Sn{sub 3}, Li{sub 5}Sn{sub 2}, Li{sub 13}Sn{sub 5}, Li{sub 7}Sn{sub 2} and Li{sub 22}Sn{sub 5}, respectively. A {delta}-{delta} correlation diagram is introduced in order to identify the different phases observed during the electrochemical process of new Sn-based materials. This approach is illustrated by the identification of the phases obtained at the end of the first discharge of {eta}-Cu{sub 6}Sn{sub 5} and SnB{sub 0.6}P{sub 0.4}O{sub 2.9}. - Graphical abstract: {delta}-{delta} correlation diagram for the different tin sites of the Li-Sn compounds. The symbols denote the different Li-Sn phases and the products obtained at the end of the discharge of {eta}-Cu{sub 6}Sn{sub 5} and SnB{sub 0.6}P{sub 0.4}O{sub 2.9}. The grey and the light-grey areas show Sn-centred polyhedra without and with one Sn first-nearest neighbours, respectively.},
doi = {10.1016/j.jssc.2006.10.026},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 180,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2007},
month = {Mon Jan 15 00:00:00 EST 2007}
}
  • The layered intercalation compounds Li(Mn{sub 1{minus}y}Co{sub y})O{sub 2}; 0 {le} y {le} 0.5 cannot be prepared by conventional solid state reaction but have been synthesized using a solution-based route coupled with ion exchange. A continuous range of solid solutions with rhombohedral symmetry exists for 0.1 {le} y {le} 0.5. Consideration of transition metal to oxygen bond lengths indicates that Mn{sup 3+} is replaced by cobalt in the trivalent state. Localized high spin Mn{sup 3+} (3d{sup 4}) induces a cooperative Jahn-Teller distortion in layered LiMnO{sub 2}, lowering the symmetry from rhombohedral R{bar 3}m to monoclinic (C2/m). Substitution of as little asmore » 10% Mn by Co is sufficient to suppress the distortion in Li{sub 0.9}(Mn{sub 0.9}Co{sub 0.1})O{sub 2}, whereas half the Li must be extracted from LiMnO{sub 2} to achieve a single undistorted rhombohedral phase. On removing and reinserting Li in LiMnO{sub 2} only half the quantity of Li (equivalent to a specific charge of 130 mAhg{sup {minus}1}) may be reinserted on the first cycle; this substantial drop in capacity is eliminated with only 10% Co substitution. The latter material can sustain a large capacity on cycling (200 mAhg{sup {minus}1}). Higher Co contents have somewhat lower capacities but fade less at higher cycle numbers. The marked improvement in capacity retention of the Co-doped materials compared with pure LiMnO{sub 2} may be related in part to the absence of the Jahn-Teller distortion. Electrochemical data indicate conversion to a spinel-like structure on cycling. Such conversion is progressively slower with increasing Co content. Cycling of this spinel-like material is significantly better than Co-doped spinel of the same composition. These materials are of interest as electrodes in rechargeable lithium batteries.« less
  • {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.more » 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.« less
  • The electrochemical reactions of lithium with layered composite electrodes ({chi})LiMn{sub 0.5}Ni{sub 0.5}O{sub 2} {center_dot} (1 - {chi})Li{sub 2}TiO{sub 3} were investigated at low voltages. The metal oxide 0.95LiMn{sub 0.5}Ni{sub 0.5}O{sub 2}{center_dot}0.05Li{sub 2}TiO{sub 3} (x=0.95) which can also be represented in layered notation as Li(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2}, can react with one equivalent of lithium during an initial discharge from 3.2 to 1.4 V vs. Li{sup 0}. The electrochemical reaction, which corresponds to a theoretical capacity of 286 mAh/g, is hypothesized to form Li{sub 2}(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2} that is isostructural with Li{sub 2}MnO{sub 2} and Li{submore » 2}NiO{sub 2}. Similar low-voltage electrochemical behavior is also observed with unsubstituted, standard LiMn{sub 0.5}Ni{sub 0.5}O{sub 2} electrodes (x=1). In situ X-ray absorption spectroscopy (XAS) data of Li(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2} electrodes indicate that the low-voltage (<1.8 V) reaction is associated primarily with the reduction of Mn{sup 4+} to Mn{sup 2+}. Symmetric rocking-chair cells with the configuration Li(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2}/Li(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2} were tested. These electrodes provide a rechargeable capacity in excess of 300 mAh/g when charged and discharged over a 3.3 to -3.3 V range and show an insignificant capacity loss on the initial cycle. These findings have implications for combating the capacity-loss effects at graphite, metal-alloy, or intermetallic negative electrodes against lithium metal-oxide positive electrodes of conventional lithium-ion cells.« less