Interplay of phase boundary anisotropy and electro-auto-catalytic surface reactions on the lithium intercalation dynamics in Li[subscript X]FePO[subscript 4] plateletlike nanoparticles
Experiments on single crystal Lip[subscript X]FePO[subscript 4] nanoparticles indicate rich nonequilibrium phase behavior, such as suppression of phase separation at high lithiation rates, striped patterns of coherent phase boundaries, and nucleation by binary-solid surface wetting and intercalation...
| Main Authors: | , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
American Physical Society
2018
|
| Online Access: | http://hdl.handle.net/1721.1/117400 https://orcid.org/0000-0003-2421-6781 https://orcid.org/0000-0002-8200-4501 |
| _version_ | 1826193960835481600 |
|---|---|
| author | Di Leo, Claudio V. Bai, Peng Nadkarni, Neel Rejovitsky, Elisha Fraggedakis, Dimitrios Smith, Raymond Barrett Bazant, Martin Z |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Di Leo, Claudio V. Bai, Peng Nadkarni, Neel Rejovitsky, Elisha Fraggedakis, Dimitrios Smith, Raymond Barrett Bazant, Martin Z |
| author_sort | Di Leo, Claudio V. |
| collection | MIT |
| description | Experiments on single crystal Lip[subscript X]FePO[subscript 4] nanoparticles indicate rich nonequilibrium phase behavior, such as suppression of phase separation at high lithiation rates, striped patterns of coherent phase boundaries, and nucleation by binary-solid surface wetting and intercalation waves. These observations have been successfully predicted (prior to the experiments) by one-dimensional (1D) depth-averaged phase-field models, which neglect any subsurface phase separation. In this paper, using an electro-chemo-mechanical phase-field model, we investigate the coherent nonequilibrium subsurface phase morphologies that develop in the ab plane of plateletlike single-crystal plateletlike Li[subscript X]FePO[subscript 4] nanoparticles. Finite element 2D plane-stress and plane-strain simulations are performed in the ab plane and validated by 3D simulations, showing similar results. Using a realistic material model from previous work, we show that the anisotropy of the interfacial tension (or gradient penalty) tensor and its relation to electro-auto-catalytic surface intercalation reactions plays a crucial role in determining the subsurface phase morphology. With the standard assumption of an isotropic interfacial tension tensor, subsurface phase separation in the bulk is observed and its morphology is independent of the reaction kinetics at the surface, but for strong anisotropy, phase separation is controlled by surface reactions, as assumed in 1D models. Moreover, the driven intercalation reaction suppresses phase separation during lithiation, while enhancing it during delithiation, by electro-auto-catalysis, in quantitative agreement with in operando imaging experiments in single-crystalline nanoparticles, given measured reaction rate constants. |
| first_indexed | 2024-09-23T09:48:00Z |
| format | Article |
| id | mit-1721.1/117400 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T09:48:00Z |
| publishDate | 2018 |
| publisher | American Physical Society |
| record_format | dspace |
| spelling | mit-1721.1/1174002022-09-26T13:50:09Z Interplay of phase boundary anisotropy and electro-auto-catalytic surface reactions on the lithium intercalation dynamics in Li[subscript X]FePO[subscript 4] plateletlike nanoparticles Di Leo, Claudio V. Bai, Peng Nadkarni, Neel Rejovitsky, Elisha Fraggedakis, Dimitrios Smith, Raymond Barrett Bazant, Martin Z Massachusetts Institute of Technology. Department of Chemical Engineering Nadkarni, Neel Rejovitsky, Elisha Fraggedakis, Dimitrios Smith, Raymond Barrett Bazant, Martin Z Experiments on single crystal Lip[subscript X]FePO[subscript 4] nanoparticles indicate rich nonequilibrium phase behavior, such as suppression of phase separation at high lithiation rates, striped patterns of coherent phase boundaries, and nucleation by binary-solid surface wetting and intercalation waves. These observations have been successfully predicted (prior to the experiments) by one-dimensional (1D) depth-averaged phase-field models, which neglect any subsurface phase separation. In this paper, using an electro-chemo-mechanical phase-field model, we investigate the coherent nonequilibrium subsurface phase morphologies that develop in the ab plane of plateletlike single-crystal plateletlike Li[subscript X]FePO[subscript 4] nanoparticles. Finite element 2D plane-stress and plane-strain simulations are performed in the ab plane and validated by 3D simulations, showing similar results. Using a realistic material model from previous work, we show that the anisotropy of the interfacial tension (or gradient penalty) tensor and its relation to electro-auto-catalytic surface intercalation reactions plays a crucial role in determining the subsurface phase morphology. With the standard assumption of an isotropic interfacial tension tensor, subsurface phase separation in the bulk is observed and its morphology is independent of the reaction kinetics at the surface, but for strong anisotropy, phase separation is controlled by surface reactions, as assumed in 1D models. Moreover, the driven intercalation reaction suppresses phase separation during lithiation, while enhancing it during delithiation, by electro-auto-catalysis, in quantitative agreement with in operando imaging experiments in single-crystalline nanoparticles, given measured reaction rate constants. Toyota Research Institute 2018-08-17T18:34:06Z 2018-08-17T18:34:06Z 2018-08 2018-06 2018-08-16T18:00:17Z Article http://purl.org/eprint/type/JournalArticle 2475-9953 http://hdl.handle.net/1721.1/117400 Nadkarni, Neel, et al. “Interplay of Phase Boundary Anisotropy and Electro-Auto-Catalytic Surface Reactions on the Lithium Intercalation Dynamics in Li[subscript X]FePO[subscript 4] Plateletlike Nanoparticles.” Physical Review Materials, vol. 2, no. 8, Aug. 2018. https://orcid.org/0000-0003-2421-6781 https://orcid.org/0000-0002-8200-4501 en http://dx.doi.org/10.1103/PhysRevMaterials.2.085406 Physical Review Materials 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. American Physical Society application/pdf American Physical Society American Physical Society |
| spellingShingle | Di Leo, Claudio V. Bai, Peng Nadkarni, Neel Rejovitsky, Elisha Fraggedakis, Dimitrios Smith, Raymond Barrett Bazant, Martin Z Interplay of phase boundary anisotropy and electro-auto-catalytic surface reactions on the lithium intercalation dynamics in Li[subscript X]FePO[subscript 4] plateletlike nanoparticles |
| title | Interplay of phase boundary anisotropy and electro-auto-catalytic surface reactions on the lithium intercalation dynamics in Li[subscript X]FePO[subscript 4] plateletlike nanoparticles |
| title_full | Interplay of phase boundary anisotropy and electro-auto-catalytic surface reactions on the lithium intercalation dynamics in Li[subscript X]FePO[subscript 4] plateletlike nanoparticles |
| title_fullStr | Interplay of phase boundary anisotropy and electro-auto-catalytic surface reactions on the lithium intercalation dynamics in Li[subscript X]FePO[subscript 4] plateletlike nanoparticles |
| title_full_unstemmed | Interplay of phase boundary anisotropy and electro-auto-catalytic surface reactions on the lithium intercalation dynamics in Li[subscript X]FePO[subscript 4] plateletlike nanoparticles |
| title_short | Interplay of phase boundary anisotropy and electro-auto-catalytic surface reactions on the lithium intercalation dynamics in Li[subscript X]FePO[subscript 4] plateletlike nanoparticles |
| title_sort | interplay of phase boundary anisotropy and electro auto catalytic surface reactions on the lithium intercalation dynamics in li subscript x fepo subscript 4 plateletlike nanoparticles |
| url | http://hdl.handle.net/1721.1/117400 https://orcid.org/0000-0003-2421-6781 https://orcid.org/0000-0002-8200-4501 |
| work_keys_str_mv | AT dileoclaudiov interplayofphaseboundaryanisotropyandelectroautocatalyticsurfacereactionsonthelithiumintercalationdynamicsinlisubscriptxfeposubscript4plateletlikenanoparticles AT baipeng interplayofphaseboundaryanisotropyandelectroautocatalyticsurfacereactionsonthelithiumintercalationdynamicsinlisubscriptxfeposubscript4plateletlikenanoparticles AT nadkarnineel interplayofphaseboundaryanisotropyandelectroautocatalyticsurfacereactionsonthelithiumintercalationdynamicsinlisubscriptxfeposubscript4plateletlikenanoparticles AT rejovitskyelisha interplayofphaseboundaryanisotropyandelectroautocatalyticsurfacereactionsonthelithiumintercalationdynamicsinlisubscriptxfeposubscript4plateletlikenanoparticles AT fraggedakisdimitrios interplayofphaseboundaryanisotropyandelectroautocatalyticsurfacereactionsonthelithiumintercalationdynamicsinlisubscriptxfeposubscript4plateletlikenanoparticles AT smithraymondbarrett interplayofphaseboundaryanisotropyandelectroautocatalyticsurfacereactionsonthelithiumintercalationdynamicsinlisubscriptxfeposubscript4plateletlikenanoparticles AT bazantmartinz interplayofphaseboundaryanisotropyandelectroautocatalyticsurfacereactionsonthelithiumintercalationdynamicsinlisubscriptxfeposubscript4plateletlikenanoparticles |