Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations
We present an ab initio study of the thermodynamics and kinetics of Li [subscript x]C[subscript 6], relevant for anode Li intercalation in rechargeable Li batteries. In graphite, the interlayer interactions are dominated by Van der Waals forces, which are not captured with standard density-functiona...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | en_US |
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American Physical Society
2011
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| Online Access: | http://hdl.handle.net/1721.1/60959 |
| _version_ | 1826206816521945088 |
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| author | Ceder, Gerbrand Persson, Kristin A. Hinuma, Yoyo Meng, Ying Shirley Van der Ven, Anton |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Ceder, Gerbrand Persson, Kristin A. Hinuma, Yoyo Meng, Ying Shirley Van der Ven, Anton |
| author_sort | Ceder, Gerbrand |
| collection | MIT |
| description | We present an ab initio study of the thermodynamics and kinetics of Li [subscript x]C[subscript 6], relevant for anode Li intercalation in rechargeable Li batteries. In graphite, the interlayer interactions are dominated by Van der Waals forces, which are not captured with standard density-functional theory (DFT). By calculating the voltage profile for Li intercalation into graphite and comparing it to experimental results, we find that only by correcting for vdW interactions between the graphene planes is it possible to reproduce the experimentally observed sequence of phases, as a function of Li content. At higher Li content the interlayer binding forces are increasingly due to Li-C interactions, which are well characterized by DFT. Using the calculated energies, corrected for the vdW interactions, we derive an ab initio lattice model, based on the cluster-expansion formalism, that accounts for interactions among Li ions in LixC6 having a stage I and stage II structure. We find that the resulting cluster expansions are dominated by Li-Li repulsive interactions. The phase diagram, obtained from Monte Carlo simulations, agrees well with experiments except at low Li concentrations as we exclude stage III and stage IV compounds. Furthermore, we calculate Li migration barriers for stage I and stage II compounds and identify limiting factors for Li mobility in the in-plane dilute as well as in the high Li concentration range. The Li diffusivity, obtained through kinetic Monte Carlo simulations, slowly decreases as a function of Li content, consistent with increasing Li-Li repulsions. However, overall we find very fast Li diffusion in bulk graphite, which may have important implications for Li battery anode optimizations. |
| first_indexed | 2024-09-23T13:39:01Z |
| format | Article |
| id | mit-1721.1/60959 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:39:01Z |
| publishDate | 2011 |
| publisher | American Physical Society |
| record_format | dspace |
| spelling | mit-1721.1/609592022-09-28T15:16:34Z Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations Ceder, Gerbrand Persson, Kristin A. Hinuma, Yoyo Meng, Ying Shirley Van der Ven, Anton Massachusetts Institute of Technology. Department of Materials Science and Engineering Ceder, Gerbrand Ceder, Gerbrand We present an ab initio study of the thermodynamics and kinetics of Li [subscript x]C[subscript 6], relevant for anode Li intercalation in rechargeable Li batteries. In graphite, the interlayer interactions are dominated by Van der Waals forces, which are not captured with standard density-functional theory (DFT). By calculating the voltage profile for Li intercalation into graphite and comparing it to experimental results, we find that only by correcting for vdW interactions between the graphene planes is it possible to reproduce the experimentally observed sequence of phases, as a function of Li content. At higher Li content the interlayer binding forces are increasingly due to Li-C interactions, which are well characterized by DFT. Using the calculated energies, corrected for the vdW interactions, we derive an ab initio lattice model, based on the cluster-expansion formalism, that accounts for interactions among Li ions in LixC6 having a stage I and stage II structure. We find that the resulting cluster expansions are dominated by Li-Li repulsive interactions. The phase diagram, obtained from Monte Carlo simulations, agrees well with experiments except at low Li concentrations as we exclude stage III and stage IV compounds. Furthermore, we calculate Li migration barriers for stage I and stage II compounds and identify limiting factors for Li mobility in the in-plane dilute as well as in the high Li concentration range. The Li diffusivity, obtained through kinetic Monte Carlo simulations, slowly decreases as a function of Li content, consistent with increasing Li-Li repulsions. However, overall we find very fast Li diffusion in bulk graphite, which may have important implications for Li battery anode optimizations. United States. ǂb Dept. of Energy. ǂb Office of FreedomCAR and Vehicle Technologies (Contract No. DEAC02- 05CH11231) Ford Motor Company (Grant No. 014502-010) National Science Foundation (U.S.) (Grant No. DMR 0748516) 2011-02-16T17:38:23Z 2011-02-16T17:38:23Z 2010-09 2010-04 Article http://purl.org/eprint/type/JournalArticle 1098-0121 1550-235X http://hdl.handle.net/1721.1/60959 Persson, Kristin et al. “Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations.” Physical Review B 82.12 (2010): n. pag. c2010 The American Physical Society en_US http://dx.doi.org/10.1103/PhysRevB.82.125416 Physical review B 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 Physical Society APS |
| spellingShingle | Ceder, Gerbrand Persson, Kristin A. Hinuma, Yoyo Meng, Ying Shirley Van der Ven, Anton Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations |
| title | Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations |
| title_full | Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations |
| title_fullStr | Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations |
| title_full_unstemmed | Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations |
| title_short | Thermodynamic and kinetic properties of the Li-graphite system from first-principles calculations |
| title_sort | thermodynamic and kinetic properties of the li graphite system from first principles calculations |
| url | http://hdl.handle.net/1721.1/60959 |
| work_keys_str_mv | AT cedergerbrand thermodynamicandkineticpropertiesoftheligraphitesystemfromfirstprinciplescalculations AT perssonkristina thermodynamicandkineticpropertiesoftheligraphitesystemfromfirstprinciplescalculations AT hinumayoyo thermodynamicandkineticpropertiesoftheligraphitesystemfromfirstprinciplescalculations AT mengyingshirley thermodynamicandkineticpropertiesoftheligraphitesystemfromfirstprinciplescalculations AT vandervenanton thermodynamicandkineticpropertiesoftheligraphitesystemfromfirstprinciplescalculations |