Synchrotron-based operando X-ray diffraction and X-ray absorption spectroscopy study of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode
Abstract Lithium-ion batteries based on high-voltage cathode materials, such as LiCoPO4, despite being promising in terms of specific power, still suffer from poor cycle life due to the lower stability of common non-aqueous electrolytes at higher voltages. One way to overcome this issue might be dec...
| Main Authors: | , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-02-01
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| Series: | Scientific Reports |
| Online Access: | https://doi.org/10.1038/s41598-023-28951-z |
| _version_ | 1811166029039009792 |
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| author | Taymour A. Hamdalla Abdelaziz M. Aboraia V. V. Shapovalov A. A. Guda N. V. Kosova O. A. Podgornova A. A. A. Darwish S. A. Al-Ghamdi S. Alfadhli Aadel M. Alatawi Alexander Soldatov |
| author_facet | Taymour A. Hamdalla Abdelaziz M. Aboraia V. V. Shapovalov A. A. Guda N. V. Kosova O. A. Podgornova A. A. A. Darwish S. A. Al-Ghamdi S. Alfadhli Aadel M. Alatawi Alexander Soldatov |
| author_sort | Taymour A. Hamdalla |
| collection | DOAJ |
| description | Abstract Lithium-ion batteries based on high-voltage cathode materials, such as LiCoPO4, despite being promising in terms of specific power, still suffer from poor cycle life due to the lower stability of common non-aqueous electrolytes at higher voltages. One way to overcome this issue might be decreasing the working potential of the battery by doping LiCoPO4 by Fe, thus reducing electrolyte degradation upon cycling. However, such modification requires a deep understanding of the structural behavior of cathode material upon lithiation/delithiation. Here we used a combination of operando synchrotron-based XRD and XAS to investigate the dynamics of d-metal local atomic structure and charge state upon cycling of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode material. Principal components analysis (PCA) of XAS data allowed the extraction of spectra of individual phases in the material and their concentrations. For both Co and Fe two components were extracted, they correspond to fully lithiated and delithiated phases of LixMPO4 (where M = Fe, Co). Thus, we were able to track the phase transitions in the material upon charge and discharge and quantitatively analyze the M2+/M3+ electrochemical conversion rate for both Fe and Co. Rietveld's refinement of XRD data allowed us to analyze the changes in the lattice of cathode material and their reversibility upon (de)lithiation during cycling. The calculation of DFT and Bader charge analysis expects the oxygen redox procedure combined with d-metals redox, which supplements iron charge variations and dominates at high voltages when x < 0.75 in LixCoFePO4. |
| first_indexed | 2024-04-10T15:45:46Z |
| format | Article |
| id | doaj.art-d5b2289c57624e638f059c7d70533b40 |
| institution | Directory Open Access Journal |
| issn | 2045-2322 |
| language | English |
| last_indexed | 2024-04-10T15:45:46Z |
| publishDate | 2023-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Scientific Reports |
| spelling | doaj.art-d5b2289c57624e638f059c7d70533b402023-02-12T12:08:46ZengNature PortfolioScientific Reports2045-23222023-02-0113111010.1038/s41598-023-28951-zSynchrotron-based operando X-ray diffraction and X-ray absorption spectroscopy study of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathodeTaymour A. Hamdalla0Abdelaziz M. Aboraia1V. V. Shapovalov2A. A. Guda3N. V. Kosova4O. A. Podgornova5A. A. A. Darwish6S. A. Al-Ghamdi7S. Alfadhli8Aadel M. Alatawi9Alexander Soldatov10Department of Physics, Faculty of Science, University of TabukPhysics Department, Faculty of Science, Al-Azhar UniversityThe Smart Materials Research Institute, Southern Federal UniversityThe Smart Materials Research Institute, Southern Federal UniversityInstitute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of SciencesInstitute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of SciencesDepartment of Physics, Faculty of Science, University of TabukDepartment of Physics, Faculty of Science, University of TabukDepartment of Physics, Faculty of Science, University of TabukElectrical Engineering Department, Faculty of Engineering, Tabuk UniversityThe Smart Materials Research Institute, Southern Federal UniversityAbstract Lithium-ion batteries based on high-voltage cathode materials, such as LiCoPO4, despite being promising in terms of specific power, still suffer from poor cycle life due to the lower stability of common non-aqueous electrolytes at higher voltages. One way to overcome this issue might be decreasing the working potential of the battery by doping LiCoPO4 by Fe, thus reducing electrolyte degradation upon cycling. However, such modification requires a deep understanding of the structural behavior of cathode material upon lithiation/delithiation. Here we used a combination of operando synchrotron-based XRD and XAS to investigate the dynamics of d-metal local atomic structure and charge state upon cycling of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode material. Principal components analysis (PCA) of XAS data allowed the extraction of spectra of individual phases in the material and their concentrations. For both Co and Fe two components were extracted, they correspond to fully lithiated and delithiated phases of LixMPO4 (where M = Fe, Co). Thus, we were able to track the phase transitions in the material upon charge and discharge and quantitatively analyze the M2+/M3+ electrochemical conversion rate for both Fe and Co. Rietveld's refinement of XRD data allowed us to analyze the changes in the lattice of cathode material and their reversibility upon (de)lithiation during cycling. The calculation of DFT and Bader charge analysis expects the oxygen redox procedure combined with d-metals redox, which supplements iron charge variations and dominates at high voltages when x < 0.75 in LixCoFePO4.https://doi.org/10.1038/s41598-023-28951-z |
| spellingShingle | Taymour A. Hamdalla Abdelaziz M. Aboraia V. V. Shapovalov A. A. Guda N. V. Kosova O. A. Podgornova A. A. A. Darwish S. A. Al-Ghamdi S. Alfadhli Aadel M. Alatawi Alexander Soldatov Synchrotron-based operando X-ray diffraction and X-ray absorption spectroscopy study of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode Scientific Reports |
| title | Synchrotron-based operando X-ray diffraction and X-ray absorption spectroscopy study of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode |
| title_full | Synchrotron-based operando X-ray diffraction and X-ray absorption spectroscopy study of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode |
| title_fullStr | Synchrotron-based operando X-ray diffraction and X-ray absorption spectroscopy study of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode |
| title_full_unstemmed | Synchrotron-based operando X-ray diffraction and X-ray absorption spectroscopy study of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode |
| title_short | Synchrotron-based operando X-ray diffraction and X-ray absorption spectroscopy study of LiCo0.5Fe0.5PO4 mixed d-metal olivine cathode |
| title_sort | synchrotron based operando x ray diffraction and x ray absorption spectroscopy study of lico0 5fe0 5po4 mixed d metal olivine cathode |
| url | https://doi.org/10.1038/s41598-023-28951-z |
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