Hostname: page-component-cd9895bd7-gbm5v Total loading time: 0 Render date: 2024-12-29T06:06:51.477Z Has data issue: false hasContentIssue false
  • English
  • Français

Tracing Reversible and Irreversible Li Insertion in SiCO Ceramics with Modeling and Ab-Initio Simulations

Published online by Cambridge University Press:  04 April 2011

Peter Kroll
Peter Kroll*
Affiliation:
Department of Chemistry and Biochemistry, The University of Texas at Arlington, 700 Planetarium Pl., 76019 Arlington, TX,
Get access

Abstract

We present combined modeling and simulation studies of Li insertion in amorphous SiCO ceramics. Atomistic models of amorphous SiCO with and without so-called “free” carbon have been crafted using a network modeling approach and subsequently relaxed and optimized within density functional theory.

In a first series, Li atoms are randomly inserted to test for sites with high binding energy. We find that Li prefers always bonding to O. The enthalpy of insertion, however, depends strongly on electronic states available in the SiCO host matrix. While Li inserted into insulating SiO2 is an energetically unfavorable process, the enthalpy of insertion in SiCO glass is decreased. Some glassy SiCO models exhibit favorable sites for Li insertion, which share a common motif in their local atomic environment. The presence of “free” carbon in SiCO then promotes Li insertion, because carbon-related structural imperfections give rise for low-lying unfilled electronic states. Consequently, strong and irreversible bonding of Li into SiCO is provided, if bonding of Li-cations in Li-O bonds outweighs the promotion energy for the electron to occupy unfilled electronic states.

Keywords

ceramicsimulationamorphous
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1313: Symposium KK – Materials for Advanced Lithium Batteries , 2011 , mrsf10-1313-kk11-07
Copyright
Copyright © Materials Research Society 2011

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1. Xing, W.; Wilson, A.M.; Eguchi, K.; Zank, G.; Dahn, J.R. J. Electrochem. Soc. 1997, 144, 2410–2416.Google Scholar
2. Sanchez-Jimenez, P E; Raj, R. J. Am. Ceram. Soc. 2010, 93, 1127–1135 Google Scholar
3. Ahn, D.; Raj, R. J Power Sources 2010, 195, 3900–3906.Google Scholar
4. Fukui, H.; Ohsuka, H.; Hino, T.; Kanamura, K.; Appl. Mater. Interface. 2010, 2, 998–1008.Google Scholar
5. Kroll, P. J Mater Chem 2003, 13, 1657 Google Scholar
6. Kroll, P. In Ceramics Science and Technology; Chen, R. R. a. I.-W., Ed.; Wiley-VCH: 2008; Vol. 1, p 41.Google Scholar
7. Kroll, P. J. Mater. Chem., 2010, DOI:10.1039/C0JM01583KGoogle Scholar