Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation

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

doi:10.1002/advs.201500057

Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation

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

Energy Storage & Conversion

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27 Scopus citations

Abstract

Silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. An electrochemical evaluation of type I silicon clathrates based on Ba₈Al_ySi_46−y as the anode material for lithium-ion batteries is presented here. Postcycling characterization with nuclear magnetic resonance and X-ray diffraction shows no discernible structural or volume changes even after electrochemical insertion of 44 Li (≈1 Li/Si) into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from large volume changes. The electrochemical reactions are proposed to occur as single phase reactions at approximately 0.2 and 0.4 V versus Li/Li⁺ during lithiation and delithiation, respectively, distinct from 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_8.54Si_37.46, corresponding to ≈1.18 Li/Si. These results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.

Original language	English
Article number	1500057
Journal	Advanced Science
Volume	2
Issue number	6
DOIs	https://doi.org/10.1002/advs.201500057
State	Published - Jun 2015

Funding

This work was supported using new faculty startup funds from the Fulton Schools of Engineering (CKC) as well as funding from NSF DMR-1206795 (CKC, YL, RR, RZ, QC, and NAW). NAW also received support from the Fulton Undergraduate Research Initiative at ASU. Part of this work was supported by the U.S. Department of Energy (DOE) through the BATT Program Contract No. DEAC0205CH11231 (KSC, MAM, CE) and the U.S. Department of Energy Office of Basic Energy Sciences Materials Sciences and Engineering Division (LB, GMV). The authors would like to thank G. Holland and B. Cherry for assistance with NMR. The authors are grateful to U. Haussermann and the Department of Chemistry at ASU for the use of their facilities. They would also acknowledge the use of facilities within the LeRoy Eyring Center for Solid State Science.

Funders	Funder number
BATT	DEAC0205CH11231
Fulton Schools of Engineering
U.S. Department of Energy Office of Basic Energy Sciences Materials Sciences and Engineering Division
National Science Foundation	DMR-1206795
U.S. Department of Energy
Directorate for Mathematical and Physical Sciences	1206795
Adams State University

Keywords

Li-ion battery
anode
silicon
ternary type I clathrate

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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title = "Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation",

abstract = "Silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. An electrochemical evaluation of type I silicon clathrates based on Ba8AlySi46−y as the anode material for lithium-ion batteries is presented here. Postcycling characterization with nuclear magnetic resonance and X-ray diffraction shows no discernible structural or volume changes even after electrochemical insertion of 44 Li (≈1 Li/Si) into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from large volume changes. The electrochemical reactions are proposed to occur as single phase reactions at approximately 0.2 and 0.4 V versus Li/Li+ during lithiation and delithiation, respectively, distinct from 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 Ba8Al8.54Si37.46, corresponding to ≈1.18 Li/Si. These results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.",

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author = "Ying Li and Rahul Raghavan and Wagner, {Nicholas A.} and Davidowski, {Stephen K.} and Lo{\"i}c Baggetto and Ran Zhao and Qian Cheng and Yarger, {Jeffery L.} and Veith, {Gabriel M.} and Carol Ellis-Terrell and Miller, {Michael A.} and Chan, {Kwai S.} and Chan, {Candace K.}",

note = "Publisher Copyright: {\textcopyright} 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Raghavan, Rahul

AU - Wagner, Nicholas A.

AU - Davidowski, Stephen K.

AU - Baggetto, Loïc

AU - Zhao, Ran

AU - Cheng, Qian

AU - Yarger, Jeffery L.

AU - Veith, Gabriel M.

AU - Ellis-Terrell, Carol

AU - Miller, Michael A.

AU - Chan, Kwai S.

AU - Chan, Candace K.

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N2 - Silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. An electrochemical evaluation of type I silicon clathrates based on Ba8AlySi46−y as the anode material for lithium-ion batteries is presented here. Postcycling characterization with nuclear magnetic resonance and X-ray diffraction shows no discernible structural or volume changes even after electrochemical insertion of 44 Li (≈1 Li/Si) into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from large volume changes. The electrochemical reactions are proposed to occur as single phase reactions at approximately 0.2 and 0.4 V versus Li/Li+ during lithiation and delithiation, respectively, distinct from 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 Ba8Al8.54Si37.46, corresponding to ≈1.18 Li/Si. These results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.

AB - Silicon clathrates contain cage-like structures that can encapsulate various guest atoms or molecules. An electrochemical evaluation of type I silicon clathrates based on Ba8AlySi46−y as the anode material for lithium-ion batteries is presented here. Postcycling characterization with nuclear magnetic resonance and X-ray diffraction shows no discernible structural or volume changes even after electrochemical insertion of 44 Li (≈1 Li/Si) into the clathrate structure. The observed properties are in stark contrast with lithiation of other silicon anodes, which become amorphous and suffer from large volume changes. The electrochemical reactions are proposed to occur as single phase reactions at approximately 0.2 and 0.4 V versus Li/Li+ during lithiation and delithiation, respectively, distinct from 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 Ba8Al8.54Si37.46, corresponding to ≈1.18 Li/Si. These results show that silicon clathrates could be promising durable anodes for lithium-ion batteries.

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Type I Clathrates as Novel Silicon Anodes: An Electrochemical and Structural Investigation

Abstract

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Keywords

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