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First principles and experimental studies of empty Si46 as anode materials for Li-ion batteries

Published online by Cambridge University Press:  17 November 2016

Kwai S. Chan ,
Michael A. Miller ,
Wuwei Liang ,
Carol Ellis-Terrell  and
Candace K. Chan
Kwai S. Chan*
Affiliation:
Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX 78238-5166, USA
Michael A. Miller
Affiliation:
Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX 78238-5166, USA
Wuwei Liang
Affiliation:
Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX 78238-5166, USA
Carol Ellis-Terrell
Affiliation:
Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX 78238-5166, USA
Candace K. Chan
Affiliation:
Materials Science and Engineering, School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ 85287-8706, USA
*
a) Address all correspondence to this author. e-mail: kchan@swri.edu
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Abstract

The objective of this investigation was to utilize the first-principles molecular dynamics computational approach to investigate the lithiation characteristics of empty silicon clathrates (Si46) for applications as potential anode materials in lithium-ion batteries. The energy of formation, volume expansion, and theoretical capacity were computed for empty silicon clathrates as a function of Li. The theoretical results were compared against experimental data of long-term cyclic tests performed on half-cells using electrodes fabricated from Si46 prepared using a Hofmann-type elimination–oxidation reaction. The comparison revealed that the theoretically predicted capacity (of 791.6 mAh/g) agreed with experimental data (809 mAh/g) that occurred after insertion of 48 Li atoms. The calculations showed that overlithiation beyond 66 Li atoms can cause large volume expansion with a volume strain as high as 120%, which may correlate to experimental observations of decreasing capacities from the maximum at 1030 mAh/g to 553 mA h/g during long-term cycling tests. The finding suggests that overlithiation beyond 66 Li atoms may have caused damage to the cage structure and led to lower reversible capacities.

Keywords

silicon clathratesLi-ion batteryanode materials

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Journal of Materials Research , Volume 31 , Issue 23 , 14 December 2016 , pp. 3657 - 3665
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Copyright © Materials Research Society 2016 

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