Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4]
A theoretical investigation of the effects of elastic coherency strain on the thermodynamics, kinetics, and morphology of intercalation in single LiFePO4 nanoparticles yields new insights into this important battery material. Anisotropic elastic stiffness and misfit strains lead to the unexpected pr...
| Main Authors: | , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2013
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| Online Access: | http://hdl.handle.net/1721.1/77925 |
| _version_ | 1826217495222026240 |
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| author | Cogswell, Daniel A. Bazant, Martin Z. |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Cogswell, Daniel A. Bazant, Martin Z. |
| author_sort | Cogswell, Daniel A. |
| collection | MIT |
| description | A theoretical investigation of the effects of elastic coherency strain on the thermodynamics, kinetics, and morphology of intercalation in single LiFePO4 nanoparticles yields new insights into this important battery material. Anisotropic elastic stiffness and misfit strains lead to the unexpected prediction that low-energy phase boundaries occur along {101} planes, while conflicting reports of phase boundary orientations are resolved by a partial loss of coherency in the [001] direction. Elastic relaxation near surfaces leads to the formation of a striped morphology with a characteristic length scale predicted by the model, yielding an estimate of the interfacial energy. The effects of coherency strain on solubility and galvanostatic discharge are studied with a reaction-limited phase-field model that quantitatively captures the influence of misfit strain, particle size, and temperature on solubility seen in experiments. Coherency strain strongly suppresses phase separation during discharge, which enhances rate capability and extends cycle life. The effects of elevated temperature and the feasibility of nucleation are considered in the context of multiparticle cathodes. |
| first_indexed | 2024-09-23T17:04:34Z |
| format | Article |
| id | mit-1721.1/77925 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T17:04:34Z |
| publishDate | 2013 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/779252022-09-29T23:29:12Z Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4] Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4] Nanoparticles Cogswell, Daniel A. Bazant, Martin Z. Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Mathematics Cogswell, Daniel A. Bazant, Martin Z. A theoretical investigation of the effects of elastic coherency strain on the thermodynamics, kinetics, and morphology of intercalation in single LiFePO4 nanoparticles yields new insights into this important battery material. Anisotropic elastic stiffness and misfit strains lead to the unexpected prediction that low-energy phase boundaries occur along {101} planes, while conflicting reports of phase boundary orientations are resolved by a partial loss of coherency in the [001] direction. Elastic relaxation near surfaces leads to the formation of a striped morphology with a characteristic length scale predicted by the model, yielding an estimate of the interfacial energy. The effects of coherency strain on solubility and galvanostatic discharge are studied with a reaction-limited phase-field model that quantitatively captures the influence of misfit strain, particle size, and temperature on solubility seen in experiments. Coherency strain strongly suppresses phase separation during discharge, which enhances rate capability and extends cycle life. The effects of elevated temperature and the feasibility of nucleation are considered in the context of multiparticle cathodes. National Science Foundation (U.S.) (Contracts DMS-0842504) National Science Foundation (U.S.) (Contracts DMS-094807) 2013-03-15T19:25:00Z 2013-03-15T19:25:00Z 2012-02 2011-10 Article http://purl.org/eprint/type/JournalArticle 1936-0851 1936-086X http://hdl.handle.net/1721.1/77925 Cogswell, Daniel A., and Martin Z. Bazant. “Coherency Strain and the Kinetics of Phase Separation in LiFePO 4.” ACS Nano 6.3 (2012): 2215–2225. en_US http://dx.doi.org/10.1021/nn204177u ACS Nano Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) arXiv |
| spellingShingle | Cogswell, Daniel A. Bazant, Martin Z. Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4] |
| title | Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4] |
| title_full | Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4] |
| title_fullStr | Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4] |
| title_full_unstemmed | Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4] |
| title_short | Coherency Strain and the Kinetics of Phase Separation in LiFePO [subscript 4] |
| title_sort | coherency strain and the kinetics of phase separation in lifepo subscript 4 |
| url | http://hdl.handle.net/1721.1/77925 |
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