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

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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.

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ACKNOWLEDGMENTS

This work was supported by the Internal Research and Development Program (Project 18.R9890) of Southwest Research Institute® (SwRI®) and the Batteries for Advanced Transportation Technologies (BATT) Program at Lawrence Berkeley National Laboratory (LBNL) through Contract No. DEAC0205CH11231, with Dr. Michel Foure at LBNL as program manager. The contribution of C.K.C. was supported by the National Science Foundation through Grant No. DMR-1206795 and startup funds from the Fulton Schools of Engineering, Arizona State University (ASU). The first principles computations were performed at the Texas Advanced Computing Center of the TerraGrid network. The authors acknowledge the clerical assistance provided by Ms. Loretta Mesa, SwRI, in the preparation of the manuscript and Ms. Ran Zhao, Ph.D. student at ASU, in the preparation of Fig. 3.

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Authors and Affiliations

  1. Department of Materials Engineering, Mechanical Engineering Division, Southwest Research Institute®, San Antonio, TX, 78238-5166, USA

    Kwai S. Chan, Michael A. Miller, Wuwei Liang & Carol Ellis-Terrell

  2. Materials Science and Engineering, School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ, 85287-8706, USA

    Candace K. Chan

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Correspondence to Kwai S. Chan.

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Chan, K.S., Miller, M.A., Liang, W. et al. First principles and experimental studies of empty Si46 as anode materials for Li-ion batteries. Journal of Materials Research 31, 3657–3665 (2016). https://doi.org/10.1557/jmr.2016.408

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