Type I clathrates as novel silicon anodes: An electrochemical and structural investigation

Li, Ying; Raghavan, Rahul; Wagner, Nicholas A.; Davidowski, Stephen K.; Baggetto, Loic; Zhao, Ran; Cheng, Qian; Yarger, Jeffery L.; Veith, Gabriel M.; Ellis-Terrell, Carol; Miller, Michael A.; Chan, Kwai S.; Chan, Candace K.

doi:10.1002/advs.201500057

Type I clathrates as novel silicon anodes: An electrochemical and structural investigation

Journal Article · Tue May 05 00:00:00 EDT 2015 · Advanced Science

DOI:https://doi.org/10.1002/advs.201500057· OSTI ID:1185934

Li, Ying ^[1]; Raghavan, Rahul ^[1]; Wagner, Nicholas A. ^[1]; Davidowski, Stephen K. ^[1]; Baggetto, Loic ^[2]; Zhao, Ran ^[1]; Cheng, Qian ^[1]; Yarger, Jeffery L. ^[1]; Veith, Gabriel M. ^[2]; Ellis-Terrell, Carol ^[3]; Miller, Michael A. ^[3]; Chan, Kwai S. ^[3]; Chan, Candace K. ^[1]

Arizona State Univ., Tempe, AZ (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Southwest Research Institute, San Antonio, TX (United States)

In this study, silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. Here we present an electrochemical evaluation of type I silicon clathrates based on Ba₈Al_ySi_46-y for the anode material in lithium-ion batteries. Post-cycling characterization with NMR and XRD show no discernible structural or volume changes even after electrochemical insertion of 44 Li into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from larger volume changes. The lithiation/delithiation processes are proposed to occur in single phase reactions at approximately 0.2 and 0.4 V vs. Li/Li⁺, respectively, distinct from other diamond cubic or amorphous silicon anodes. Reversible capacities as high as 499 mAh g^-1 at a 5 mA g^-1 rate were observed for silicon clathrate with composition Ba₈Al_8.54S_i37.46, corresponding to Li:Si of 1.18:1. The results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1185934

Journal Information:: Advanced Science, Journal Name: Advanced Science Journal Issue: 6 Vol. 2; ISSN 2198-3844

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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