Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4
The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the sub...
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American Chemical Society
2019
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| Online-Zugang: | https://demo7.dspace.org/handle/123456789/445 |
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| author | Strobridge, Fiona C Liu, Hao Leskes, Michal Borkiewicz, Olaf J Wiaderek, Kamila M Chupas, Peter J Chapman, Karena W Grey, Clare |
| author2 | Plasma, Laser Ablation and Surface Modelling - Antwerp (PLASMANT) |
| author_browse | Borkiewicz, Olaf J Chapman, Karena W Chupas, Peter J Grey, Clare Leskes, Michal Liu, Hao Plasma, Laser Ablation and Surface Modelling - Antwerp (PLASMANT) Strobridge, Fiona C Wiaderek, Kamila M |
| author_facet | Plasma, Laser Ablation and Surface Modelling - Antwerp (PLASMANT) Strobridge, Fiona C Liu, Hao Leskes, Michal Borkiewicz, Olaf J Wiaderek, Kamila M Chupas, Peter J Chapman, Karena W Grey, Clare |
| author_sort | Strobridge, Fiona C |
| collection | DSpace |
| description | The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95 and 1) are electrochemically cycled is reported here, using in situ X-ray diffraction (XRD) data, and supporting ex situ 31P NMR spectra. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)x(Co2+)1-xPO4 for 0 < x < 1 (i.e. after oxidation of Fe2+ => Fe3+) and Li2/3FexCo1-xPO4 for 0 ≤ x ≤ 0.5 (i.e. the Co-majority materials). For the Fe-rich materials, we study how nonequilibrium, single-phase mechanisms that occur discretely in single particles, as observed for LiFePO4 at high rates, are affected by Co substitution. In the Co-majority materials, a two-phase mechanism with a coherent interface is observed, as was seen in LiCoPO4, and we discuss how it is manifested in the XRD patterns. We then compare the nonequilibrium, single-phase mechanism with the bulk single-phase and the coherent interface two-phase mechanisms. Despite the apparent differences between these mechanisms, we discuss how they are related and interconverted as a function of Fe/Co substitution and the potential implications for the electrochemistry of this system. |
| id | oai:localhost:123456789-445 |
| institution | DSPACE.FCHPT |
| language | English |
| publishDate | 2019 |
| publishDateRange | 2019 |
| publishDateSort | 2019 |
| publisher | American Chemical Society |
| publisherStr | American Chemical Society |
| record_format | dspace |
| spelling | oai:localhost:123456789-4452021-04-07T16:30:12Z Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4 Strobridge, Fiona C Liu, Hao Leskes, Michal Borkiewicz, Olaf J Wiaderek, Kamila M Chupas, Peter J Chapman, Karena W Grey, Clare Plasma, Laser Ablation and Surface Modelling - Antwerp (PLASMANT) The delithiation mechanisms occurring within the olivine-type class of cathode materials for Li-ion batteries have received considerable attention owing to the good capacity retention at high rates for LiFePO4. A comprehensive mechanistic study of the (de)lithiation reactions that occur when the substituted olivine-type cathode materials LiFexCo1-xPO4 (x = 0, 0.05, 0.125, 0.25, 0.5, 0.75, 0.875, 0.95 and 1) are electrochemically cycled is reported here, using in situ X-ray diffraction (XRD) data, and supporting ex situ 31P NMR spectra. On the first charge, two intermediate phases are observed and identified: Li1-x(Fe3+)x(Co2+)1-xPO4 for 0 < x < 1 (i.e. after oxidation of Fe2+ => Fe3+) and Li2/3FexCo1-xPO4 for 0 ≤ x ≤ 0.5 (i.e. the Co-majority materials). For the Fe-rich materials, we study how nonequilibrium, single-phase mechanisms that occur discretely in single particles, as observed for LiFePO4 at high rates, are affected by Co substitution. In the Co-majority materials, a two-phase mechanism with a coherent interface is observed, as was seen in LiCoPO4, and we discuss how it is manifested in the XRD patterns. We then compare the nonequilibrium, single-phase mechanism with the bulk single-phase and the coherent interface two-phase mechanisms. Despite the apparent differences between these mechanisms, we discuss how they are related and interconverted as a function of Fe/Co substitution and the potential implications for the electrochemistry of this system. 2019-04-26T08:57:03Z 2019-04-26T08:57:03Z 25/04/16 https://demo7.dspace.org/handle/123456789/445 en American Chemical Society |
| spellingShingle | Strobridge, Fiona C Liu, Hao Leskes, Michal Borkiewicz, Olaf J Wiaderek, Kamila M Chupas, Peter J Chapman, Karena W Grey, Clare Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4 |
| title | Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4 |
| title_full | Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4 |
| title_fullStr | Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4 |
| title_full_unstemmed | Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4 |
| title_short | Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFexCo1-xPO4 |
| title_sort | unraveling the complex delithiation mechanisms of olivine type cathode materials lifexco1 xpo4 |
| url | https://demo7.dspace.org/handle/123456789/445 |
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