Sn{sub x}[BPO{sub 4}]{sub 1-x} composites as negative electrodes for lithium ion cells: Comparison with amorphous SnB{sub 0.6}P{sub 0.4}O{sub 2.9} and effect of composition

Journal Article · Fri Jan 15 00:00:00 EST 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.10.015· OSTI ID:21372450

Aboulaich, Abdelmaula; Robert, Florent; Olivier-Fourcade, Josette; Jumas, Jean-Claude ^[1]; Jordy, Christian ^[2]; Willmann, Patrick ^[3]

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1. Institut Charles Gerhardt-Equipe Agregats, Interfaces et Materiaux pour l'Energie, UMR 5253-CNRS, Universite Montpellier II, Place E. Bataillon, 34095 Montpellier (France)
2. SAFT, 111-113 Bd. A. Daney, 33074 Bordeaux Cedex (France)
3. CNES, Centre Spatial de Toulouse, 18 Avenue Edouard Belin, 31401 Toulouse (France)

A comparative study of two Sn-based composite materials as negative electrode for Li-ion accumulators is presented. The former SnB{sub 0.6}P{sub 0.4}O{sub 2.9} obtained by in-situ dispersion of SnO in an oxide matrix is shown to be an amorphous tin composite oxide (ATCO). The latter Sn{sub 0.72}[BPO{sub 4}]{sub 0.28} obtained by ex-situ dispersion of Sn in a borophosphate matrix consists of Sn particles embedded in a crystalline BPO{sub 4} matrix. The electrochemical responses of ATCO and Sn{sub 0.72}[BPO{sub 4}]{sub 0.28} composite in galvanostatic mode show reversible capacities of about 450 and 530 mAh g{sup -1}, respectively, with different irreversible capacities (60% and 29%). Analysis of these composite materials by {sup 119}Sn Moessbauer spectroscopy in transmission (TMS) and emission (CEMS) modes confirms that ATCO is an amorphous Sn{sup II} composite oxide and shows that in the case of Sn{sub 0.72}[BPO{sub 4}]{sub 0.28}, the surface of the tin clusters is mainly formed by Sn{sup II} in an amorphous interface whereas the bulk of the clusters is mainly formed by Sn{sup 0}. The determination of the recoilless free fractions f (Lamb-Moessbauer factors) leads to the effective fraction of both Sn{sup 0} and Sn{sup II} species in such composites. The influence of chemical composition and especially of the surface-to-bulk tin species ratio on the electrochemical behaviour has been analysed for several Sn{sub x}[BPO{sub 4}]{sub 1-x} composite materials (0.17<x<0.91). The cell using the compound Sn{sub 0.72}[BPO{sub 4}]{sub 0.28} as active material exhibits interesting electrochemical performances (reversible capacity of 500 mAh g{sup -1} at C/5 rate). - Abstract: Galvanostatic discharge-charge curves of ATCO and Sn{sub 0.72}[BPO{sub 4}]{sub 0.28} composite materials at C/5 rate, respectively.

• OSTI ID: 21372450
• Journal Information: Journal of Solid State Chemistry, Vol. 183, Issue 1; Other Information: DOI: 10.1016/j.jssc.2009.10.015; PII: S0022-4596(09)00499-X; 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
ANODES
BORON PHOSPHATES
CHEMICAL COMPOSITION
COMPOSITE MATERIALS
DISPERSIONS
ELECTRIC BATTERIES
ELECTROCHEMISTRY
LITHIUM IONS
MOESSBAUER EFFECT
TIN COMPOUNDS
TIN OXIDES
BORON COMPOUNDS
CHALCOGENIDES
CHARGED PARTICLES
CHEMISTRY
ELECTROCHEMICAL CELLS
ELECTRODES
ENERGY STORAGE SYSTEMS
ENERGY SYSTEMS
IONS
MATERIALS
OXIDES
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS