Anomalous Shape Changes of Silicon Nanopillars by Electrochemical Lithiation

Handle URI:
http://hdl.handle.net/10754/597583
Title:
Anomalous Shape Changes of Silicon Nanopillars by Electrochemical Lithiation
Authors:
Lee, Seok Woo; McDowell, Matthew T.; Choi, Jang Wook; Cui, Yi
Abstract:
Silicon is one of the most attractive anode materials for use in Li-ion batteries due to its ∼10 times higher specific capacity than existing graphite anodes. However, up to 400% volume expansion during reaction with Li causes particle pulverization and fracture, which results in rapid capacity fading. Although Si nanomaterials have shown improvements in electrochemical performance, there is limited understanding of how volume expansion takes place. Here, we study the shape and volume changes of crystalline Si nanopillars with different orientations upon first lithiation and discover anomalous behavior. Upon lithiation, the initially circular cross sections of nanopillars with 〈100〉, 〈110〉, and 〈111〉 axial orientations expand into cross, ellipse, and hexagonal shapes, respectively. We explain this by identifying a high-speed lithium ion diffusion channel along the 〈110〉 direction, which causes preferential volume expansion along this direction. Surprisingly, the 〈111〉 and 〈100〉 nanopillars shrink in height after partial lithiation, while 〈110〉 nanopillars increase in height. The length contraction is suggested to be due to a collapse of the {111} planes early in the lithiation process. These results give new insight into the Si volume change process and could help in designing better battery anodes. © 2011 American Chemical Society.
Citation:
Lee SW, McDowell MT, Choi JW, Cui Y (2011) Anomalous Shape Changes of Silicon Nanopillars by Electrochemical Lithiation. Nano Lett 11: 3034–3039. Available: http://dx.doi.org/10.1021/nl201787r.
Publisher:
American Chemical Society (ACS)
Journal:
Nano Letters
KAUST Grant Number:
KUS-11-001-12; KUK-F1-038-02
Issue Date:
13-Jul-2011
DOI:
10.1021/nl201787r
PubMed ID:
21657250
Type:
Article
ISSN:
1530-6984; 1530-6992
Sponsors:
This work is partially supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under contract DE-AC02-76SF0051 through the SLAC National Accelerator Laboratory LDRD project. Y.C. acknowledges support from the King Abdullah University of Science and Technology (KAUST) Investigator Award (No. KUS-11-001-12). S.W.L. acknowledges support from KAUST (Award No. KUK-F1-038-02). M.T.M. acknowledges support from the Chevron Stanford Graduate Fellowship, the National Defense Science and Engineering Graduate Fellowship, and the National Science Foundation Graduate Fellowship. J.W. C. acknowledges the National Research Foundation of Korea Grant funded by the Korean Government (MEST) for the financial support through the Secondary Battery Program (NRF-2010-0029031) and the World Class University Program for the financial support (R-31-2008-000-10055-0).
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Full metadata record

DC FieldValue Language
dc.contributor.authorLee, Seok Wooen
dc.contributor.authorMcDowell, Matthew T.en
dc.contributor.authorChoi, Jang Wooken
dc.contributor.authorCui, Yien
dc.date.accessioned2016-02-25T12:42:30Zen
dc.date.available2016-02-25T12:42:30Zen
dc.date.issued2011-07-13en
dc.identifier.citationLee SW, McDowell MT, Choi JW, Cui Y (2011) Anomalous Shape Changes of Silicon Nanopillars by Electrochemical Lithiation. Nano Lett 11: 3034–3039. Available: http://dx.doi.org/10.1021/nl201787r.en
dc.identifier.issn1530-6984en
dc.identifier.issn1530-6992en
dc.identifier.pmid21657250en
dc.identifier.doi10.1021/nl201787ren
dc.identifier.urihttp://hdl.handle.net/10754/597583en
dc.description.abstractSilicon is one of the most attractive anode materials for use in Li-ion batteries due to its ∼10 times higher specific capacity than existing graphite anodes. However, up to 400% volume expansion during reaction with Li causes particle pulverization and fracture, which results in rapid capacity fading. Although Si nanomaterials have shown improvements in electrochemical performance, there is limited understanding of how volume expansion takes place. Here, we study the shape and volume changes of crystalline Si nanopillars with different orientations upon first lithiation and discover anomalous behavior. Upon lithiation, the initially circular cross sections of nanopillars with 〈100〉, 〈110〉, and 〈111〉 axial orientations expand into cross, ellipse, and hexagonal shapes, respectively. We explain this by identifying a high-speed lithium ion diffusion channel along the 〈110〉 direction, which causes preferential volume expansion along this direction. Surprisingly, the 〈111〉 and 〈100〉 nanopillars shrink in height after partial lithiation, while 〈110〉 nanopillars increase in height. The length contraction is suggested to be due to a collapse of the {111} planes early in the lithiation process. These results give new insight into the Si volume change process and could help in designing better battery anodes. © 2011 American Chemical Society.en
dc.description.sponsorshipThis work is partially supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under contract DE-AC02-76SF0051 through the SLAC National Accelerator Laboratory LDRD project. Y.C. acknowledges support from the King Abdullah University of Science and Technology (KAUST) Investigator Award (No. KUS-11-001-12). S.W.L. acknowledges support from KAUST (Award No. KUK-F1-038-02). M.T.M. acknowledges support from the Chevron Stanford Graduate Fellowship, the National Defense Science and Engineering Graduate Fellowship, and the National Science Foundation Graduate Fellowship. J.W. C. acknowledges the National Research Foundation of Korea Grant funded by the Korean Government (MEST) for the financial support through the Secondary Battery Program (NRF-2010-0029031) and the World Class University Program for the financial support (R-31-2008-000-10055-0).en
dc.publisherAmerican Chemical Society (ACS)en
dc.subjectanisotropic propertiesen
dc.subjectLithium-ion batteryen
dc.subjectphase changeen
dc.subjectsilicon anodeen
dc.titleAnomalous Shape Changes of Silicon Nanopillars by Electrochemical Lithiationen
dc.typeArticleen
dc.identifier.journalNano Lettersen
dc.contributor.institutionStanford University, Palo Alto, United Statesen
dc.contributor.institutionKorea Advanced Institute of Science & Technology, Yusong, South Koreaen
kaust.grant.numberKUS-11-001-12en
kaust.grant.numberKUK-F1-038-02en

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