Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structure
According to the extensive studies in the field of high-energy cathode materials for lithium-ion batteries (LIBs), Mn-based oxyfluorides Li1.2Mn0.6+0.5yNb0.2–0.5yO2–yFy with Li-excess and cation-disordered rock-salt structure capable of reversible cationic and anionic redox reactions are among the m...
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Uralʹskij federalʹnyj universitet imeni pervogo Prezidenta Rossii B.N. Elʹcina
2022-08-01
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| Series: | Chimica Techno Acta |
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| Online Access: | https://chimicatechnoacta.ru/article/view/6013 |
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| author | Kseniya V. Mishchenko Maria A. Kirsanova Arseny B. Slobodyuk Anna A. Krinitsyna Nina V. Kosova |
| author_facet | Kseniya V. Mishchenko Maria A. Kirsanova Arseny B. Slobodyuk Anna A. Krinitsyna Nina V. Kosova |
| author_sort | Kseniya V. Mishchenko |
| collection | DOAJ |
| description | According to the extensive studies in the field of high-energy cathode materials for lithium-ion batteries (LIBs), Mn-based oxyfluorides Li1.2Mn0.6+0.5yNb0.2–0.5yO2–yFy with Li-excess and cation-disordered rock-salt structure capable of reversible cationic and anionic redox reactions are among the most promising candidates. In this work, a series of Mn-based oxyfluorides with y = 0.05, 0.10, 0.15 were obtained using mechanochemically assisted solid-state synthesis with different cooling rates. Transmission electron microscopy, electron paramagnetic spectroscopy (EPR) and nuclear magnetic resonance spectroscopy (NMR) show that increasing the amount of fluorine promotes local ordering in crystals with the formation of isolated clusters of Mn3+–O2––Mn4+ that interrupt lithium diffusion. The occurrence of local ordering depends on the conditions of synthesis and affects electrochemistry. It was found that more clusters are formed in slowly cooled samples than in quenched ones. The best electrochemical characteristics with reversible capacity of 150 mAh·g–1 at room temperature were demonstrated by the Li1.2Mn0.65Nb0.15O0.90F0.10 sample obtained by quenching. |
| format | Article |
| id | doaj-art-4ad655c03e52464d8a0dd3a1a9044813 |
| institution | Kabale University |
| issn | 2411-1414 |
| language | English |
| publishDate | 2022-08-01 |
| publisher | Uralʹskij federalʹnyj universitet imeni pervogo Prezidenta Rossii B.N. Elʹcina |
| record_format | Article |
| series | Chimica Techno Acta |
| spelling | doaj-art-4ad655c03e52464d8a0dd3a1a90448132024-12-25T09:36:55ZengUralʹskij federalʹnyj universitet imeni pervogo Prezidenta Rossii B.N. ElʹcinaChimica Techno Acta2411-14142022-08-019310.15826/chimtech.2022.9.3.104529Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structureKseniya V. Mishchenko0Maria A. Kirsanova1Arseny B. Slobodyuk2Anna A. Krinitsyna3Nina V. Kosova4Institute of Solid State Chemistry and Mechanochemistry SB RASSkolkovo Institute of Science and TechnologyInstitute of Chemistry FEB RASInstitute of Solid State Chemistry and Mechanochemistry SB RASInstitute of Solid State Chemistry and Mechanochemistry SB RASAccording to the extensive studies in the field of high-energy cathode materials for lithium-ion batteries (LIBs), Mn-based oxyfluorides Li1.2Mn0.6+0.5yNb0.2–0.5yO2–yFy with Li-excess and cation-disordered rock-salt structure capable of reversible cationic and anionic redox reactions are among the most promising candidates. In this work, a series of Mn-based oxyfluorides with y = 0.05, 0.10, 0.15 were obtained using mechanochemically assisted solid-state synthesis with different cooling rates. Transmission electron microscopy, electron paramagnetic spectroscopy (EPR) and nuclear magnetic resonance spectroscopy (NMR) show that increasing the amount of fluorine promotes local ordering in crystals with the formation of isolated clusters of Mn3+–O2––Mn4+ that interrupt lithium diffusion. The occurrence of local ordering depends on the conditions of synthesis and affects electrochemistry. It was found that more clusters are formed in slowly cooled samples than in quenched ones. The best electrochemical characteristics with reversible capacity of 150 mAh·g–1 at room temperature were demonstrated by the Li1.2Mn0.65Nb0.15O0.90F0.10 sample obtained by quenching.https://chimicatechnoacta.ru/article/view/6013lithium-ion batteriesoxyfluoridesdisordered rock-salt structurelocal orderingoxygen redoxmn3+/mn4+ redoxcyclability |
| spellingShingle | Kseniya V. Mishchenko Maria A. Kirsanova Arseny B. Slobodyuk Anna A. Krinitsyna Nina V. Kosova Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structure Chimica Techno Acta lithium-ion batteries oxyfluorides disordered rock-salt structure local ordering oxygen redox mn3+/mn4+ redox cyclability |
| title | Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structure |
| title_full | Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structure |
| title_fullStr | Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structure |
| title_full_unstemmed | Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structure |
| title_short | Effect of cooling rate on the structure and electrochemical properties of Mn-based oxyfluorides with cation-disordered rock-salt structure |
| title_sort | effect of cooling rate on the structure and electrochemical properties of mn based oxyfluorides with cation disordered rock salt structure |
| topic | lithium-ion batteries oxyfluorides disordered rock-salt structure local ordering oxygen redox mn3+/mn4+ redox cyclability |
| url | https://chimicatechnoacta.ru/article/view/6013 |
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