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Stable SiOC/Sn Nanocomposite Anodes for Lithium-Ion Batteries with Outstanding Cycling Stability

Kaspar, Jan and Terzioglu, Caglar and Ionescu, Emanuel and Graczyk-Zajac, Magdalena and Hapis, Stefania and Kleebe, Hans-Joachim and Riedel, Ralf (2014):
Stable SiOC/Sn Nanocomposite Anodes for Lithium-Ion Batteries with Outstanding Cycling Stability.
In: Advanced Functional Materials, pp. 4097-4104, 24, (26), ISSN 1616301X,
[Online-Edition: http://dx.doi.org/10.1002/adfm.201303828],
[Article]

Abstract

Silicon oxycarbide/tin nanocomposites (SiOC/Sn) are prepared by chemical modification of polysilsesquioxane Wacker-Belsil PMS MK (SiOCMK) and polysiloxane Polyramic RD-684a (SiOCRD) with tin(II)acetate and subsequent pyrolysis at 1000 °C. The obtained samples consist of an amorphous SiOC matrix and in-situ formed metallic Sn precipitates. Galvanostatic cycling of both composites demonstrate a first cycle reversible capacity of 566 mAhg−1 for SiOCMK/Sn and 651 mAhg−1 for SiOCRD/Sn. The superior cycling stability and rate capability of SiOCRD/Sn as compared to SiOCMK/Sn is attributed to the soft, carbon-rich SiOC matrix derived from the RD-684a polymer, which accommodates the Sn-related volume changes during Li-uptake and release. The poor cycling stability found for SiOCMK/Sn relates to mechanical failure of the rather stiff and fragile, carbon-poor matrix produced from PMS MK. Incremental capacity measurements outline different final Li–Sn alloy stages, depending on the matrix. For SiOCRD/Sn, alloying up to Li7Sn2 is registered, whereas for SiOCMK/Sn Li22Sn5 stoichiometry is reached. The suppression of Li22Sn5 phase in SiOCRD/Sn is rationalized by an expansion restriction of the matrix and thus prevention of a higher Li content in the alloy. For SiOCMK/Sn on the contrary, the matrix severely ruptures, providing an unlimited free volume for expansion and thus formation of Li22Sn5 phase.

Item Type: Article
Erschienen: 2014
Creators: Kaspar, Jan and Terzioglu, Caglar and Ionescu, Emanuel and Graczyk-Zajac, Magdalena and Hapis, Stefania and Kleebe, Hans-Joachim and Riedel, Ralf
Title: Stable SiOC/Sn Nanocomposite Anodes for Lithium-Ion Batteries with Outstanding Cycling Stability
Language: English
Abstract:

Silicon oxycarbide/tin nanocomposites (SiOC/Sn) are prepared by chemical modification of polysilsesquioxane Wacker-Belsil PMS MK (SiOCMK) and polysiloxane Polyramic RD-684a (SiOCRD) with tin(II)acetate and subsequent pyrolysis at 1000 °C. The obtained samples consist of an amorphous SiOC matrix and in-situ formed metallic Sn precipitates. Galvanostatic cycling of both composites demonstrate a first cycle reversible capacity of 566 mAhg−1 for SiOCMK/Sn and 651 mAhg−1 for SiOCRD/Sn. The superior cycling stability and rate capability of SiOCRD/Sn as compared to SiOCMK/Sn is attributed to the soft, carbon-rich SiOC matrix derived from the RD-684a polymer, which accommodates the Sn-related volume changes during Li-uptake and release. The poor cycling stability found for SiOCMK/Sn relates to mechanical failure of the rather stiff and fragile, carbon-poor matrix produced from PMS MK. Incremental capacity measurements outline different final Li–Sn alloy stages, depending on the matrix. For SiOCRD/Sn, alloying up to Li7Sn2 is registered, whereas for SiOCMK/Sn Li22Sn5 stoichiometry is reached. The suppression of Li22Sn5 phase in SiOCRD/Sn is rationalized by an expansion restriction of the matrix and thus prevention of a higher Li content in the alloy. For SiOCMK/Sn on the contrary, the matrix severely ruptures, providing an unlimited free volume for expansion and thus formation of Li22Sn5 phase.

Journal or Publication Title: Advanced Functional Materials
Volume: 24
Number: 26
Uncontrolled Keywords: Li-ion batteries; silicon oxycarbide; tin; nanocomposites; anode materials
Divisions: 11 Department of Materials and Earth Sciences > Earth Science > Geo-Material-Science
11 Department of Materials and Earth Sciences > Material Science > Dispersive Solids
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > A - Synthesis > Subproject A4: Novel functional ceramics using anionic substitution in oxidic systems
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > B - Characterisation > Subproject B3: Structure Characterization of Piezoelectric Ceramics With Respect to Electrical Fatigue
11 Department of Materials and Earth Sciences > Earth Science
11 Department of Materials and Earth Sciences > Material Science
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > A - Synthesis
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue > B - Characterisation
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 595: Electrical fatigue
11 Department of Materials and Earth Sciences
Zentrale Einrichtungen
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres
DFG-Collaborative Research Centres (incl. Transregio)
Date Deposited: 15 Jul 2014 08:16
Official URL: http://dx.doi.org/10.1002/adfm.201303828
Additional Information:

SFB 595 cooperation A4, B3

Identification Number: doi:10.1002/adfm.201303828
Funders: This work was finanicially supported by the Deutsche Forschungsgemeinschaft (DFG), Bonn, Germany within SPP1473/JP8, SPP1181 and SFB595 programs..
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