Intercalation Kinetics in Multiphase-Layered Materials
Many intercalation compounds possess layered structures or interpenetrating lattices that enable phase separation into three or more stable phases, or "stages," driven by competing intralayer and interlayer forces. While these structures are often well characterized in equilibrium, their e...
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| Format: | Article |
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/118875 https://orcid.org/0000-0003-2421-6781 https://orcid.org/0000-0002-3171-7982 https://orcid.org/0000-0002-8200-4501 |
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| author | Smith, Raymond Barrett Khoo, Edwin Sze Lun Bazant, Martin Z |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Smith, Raymond Barrett Khoo, Edwin Sze Lun Bazant, Martin Z |
| author_sort | Smith, Raymond Barrett |
| collection | MIT |
| description | Many intercalation compounds possess layered structures or interpenetrating lattices that enable phase separation into three or more stable phases, or "stages," driven by competing intralayer and interlayer forces. While these structures are often well characterized in equilibrium, their effects on intercalation kinetics and transport far from equilibrium are typically neglected or approximated by empirical solid solution models. Here, we formulate a general phase-field model with thermodynamically consistent reaction kinetics and cooperative transport to capture the dynamics of intercalation in layered materials. As an important case for Li-ion batteries, we model single particles of lithium intercalated graphite as having a periodic two-layer structure with three stable phases, corresponding to zero, one, or two layers full of lithium. The electrochemical intercalation reaction is described by a generalized Butler-Volmer equation with thermodynamic factors to account for the flexible structure of the graphene planes. The model naturally captures the "voltage staircase" discharge curves as a result of staging dynamics with internal "checkerboard" domains, which cannot be described by solid-solution models based on Fickian diffusion. On the other hand, the two-layer model is computationally expensive and excludes low-density stable phases with longer-range periodicity, so we also present a reduced model for graphite, which captures the high-density stages while fitting the low-density voltage profile as an effective solid solution. The two models illustrate the general trade-off between the explicit modeling of periodic layers or lattices and the needs for computational efficiency and accurate fitting of experimental data. |
| first_indexed | 2024-09-23T12:34:03Z |
| format | Article |
| id | mit-1721.1/118875 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T12:34:03Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1188752022-09-28T08:41:29Z Intercalation Kinetics in Multiphase-Layered Materials Smith, Raymond Barrett Khoo, Edwin Sze Lun Bazant, Martin Z Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Mathematics Khoo, Edwin Smith, Raymond Barrett Khoo, Edwin Sze Lun Bazant, Martin Z Many intercalation compounds possess layered structures or interpenetrating lattices that enable phase separation into three or more stable phases, or "stages," driven by competing intralayer and interlayer forces. While these structures are often well characterized in equilibrium, their effects on intercalation kinetics and transport far from equilibrium are typically neglected or approximated by empirical solid solution models. Here, we formulate a general phase-field model with thermodynamically consistent reaction kinetics and cooperative transport to capture the dynamics of intercalation in layered materials. As an important case for Li-ion batteries, we model single particles of lithium intercalated graphite as having a periodic two-layer structure with three stable phases, corresponding to zero, one, or two layers full of lithium. The electrochemical intercalation reaction is described by a generalized Butler-Volmer equation with thermodynamic factors to account for the flexible structure of the graphene planes. The model naturally captures the "voltage staircase" discharge curves as a result of staging dynamics with internal "checkerboard" domains, which cannot be described by solid-solution models based on Fickian diffusion. On the other hand, the two-layer model is computationally expensive and excludes low-density stable phases with longer-range periodicity, so we also present a reduced model for graphite, which captures the high-density stages while fitting the low-density voltage profile as an effective solid solution. The two models illustrate the general trade-off between the explicit modeling of periodic layers or lattices and the needs for computational efficiency and accurate fitting of experimental data. 2018-11-05T15:09:43Z 2018-11-05T15:09:43Z 2017-06 2017-01 2018-11-01T17:40:21Z Article http://purl.org/eprint/type/JournalArticle 1932-7447 1932-7455 http://hdl.handle.net/1721.1/118875 Smith, Raymond B. et al. “Intercalation Kinetics in Multiphase-Layered Materials.” The Journal of Physical Chemistry C 121, 23 (June 2017): 12505–12523 © 2017 American Chemical Society https://orcid.org/0000-0003-2421-6781 https://orcid.org/0000-0002-3171-7982 https://orcid.org/0000-0002-8200-4501 http://dx.doi.org/10.1021/ACS.JPCC.7B00185 Journal of Physical Chemistry C 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 | Smith, Raymond Barrett Khoo, Edwin Sze Lun Bazant, Martin Z Intercalation Kinetics in Multiphase-Layered Materials |
| title | Intercalation Kinetics in Multiphase-Layered Materials |
| title_full | Intercalation Kinetics in Multiphase-Layered Materials |
| title_fullStr | Intercalation Kinetics in Multiphase-Layered Materials |
| title_full_unstemmed | Intercalation Kinetics in Multiphase-Layered Materials |
| title_short | Intercalation Kinetics in Multiphase-Layered Materials |
| title_sort | intercalation kinetics in multiphase layered materials |
| url | http://hdl.handle.net/1721.1/118875 https://orcid.org/0000-0003-2421-6781 https://orcid.org/0000-0002-3171-7982 https://orcid.org/0000-0002-8200-4501 |
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