Theoretical Study Using First-Principles Calculations of the Electronic Structures of Magnesium Secondary Battery Cathode Materials MgCo2−xMnxO4 (x = 0, 0.5) in the Pristine and Discharged States
In this study, the projected density of states (PDOS) of the stable normal-spinel structure and stable Mg/Co mixed-cation spinel structure of Mg1+yCo2−xMnxO4 (x = 0, 0.5; y = 0, 0.5, 1) in the pristine and discharged states are obtained using first-principles calculations. The spin state and the val...
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| Format: | Article |
| Language: | English |
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The Electrochemical Society of Japan
2021-05-01
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| Series: | Electrochemistry |
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| Online Access: | https://www.jstage.jst.go.jp/article/electrochemistry/89/3/89_21-00024/_pdf/-char/en |
| _version_ | 1797972053304803328 |
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| author | Chiaki ISHIBASHI Mai ICHIYAMA Naoya ISHIDA Naoto KITAMURA Yasushi IDEMOTO |
| author_facet | Chiaki ISHIBASHI Mai ICHIYAMA Naoya ISHIDA Naoto KITAMURA Yasushi IDEMOTO |
| author_sort | Chiaki ISHIBASHI |
| collection | DOAJ |
| description | In this study, the projected density of states (PDOS) of the stable normal-spinel structure and stable Mg/Co mixed-cation spinel structure of Mg1+yCo2−xMnxO4 (x = 0, 0.5; y = 0, 0.5, 1) in the pristine and discharged states are obtained using first-principles calculations. The spin state and the valence state of the transition metals are investigated. The overlaps of the d orbitals of the transition metals and the p orbitals of oxygen are large, and the covalency between the transition metal and oxygen is strong in the pristine MgCo2O4 and MgCo1.5Mn0.5O4. The M–O6 (M = Co, Mn) octahedra become stable as a host structure. From the PDOS spectra, Co atoms are in the trivalent low-spin state in pristine MgCo2O4 and MgCo1.5Mn0.5O4 and Mn atoms are nearly tetravalent in pristine MgCo1.5Mn0.5O4. In the discharge process, the overlap of the d orbitals of the transition metals and the p orbitals of oxygen becomes narrow and the valence of the transition metals decreases with increasing Mg insertion. The results of the first-principles calculations are consistent with those of X-ray absorption near edge structure spectra. |
| first_indexed | 2024-04-11T03:41:16Z |
| format | Article |
| id | doaj.art-98f8e0e6ea2f4526bae416714c76dd6d |
| institution | Directory Open Access Journal |
| issn | 2186-2451 |
| language | English |
| last_indexed | 2024-04-11T03:41:16Z |
| publishDate | 2021-05-01 |
| publisher | The Electrochemical Society of Japan |
| record_format | Article |
| series | Electrochemistry |
| spelling | doaj.art-98f8e0e6ea2f4526bae416714c76dd6d2023-01-02T03:40:14ZengThe Electrochemical Society of JapanElectrochemistry2186-24512021-05-0189325626610.5796/electrochemistry.21-00024electrochemistryTheoretical Study Using First-Principles Calculations of the Electronic Structures of Magnesium Secondary Battery Cathode Materials MgCo2−xMnxO4 (x = 0, 0.5) in the Pristine and Discharged StatesChiaki ISHIBASHI0Mai ICHIYAMA1Naoya ISHIDA2Naoto KITAMURA3Yasushi IDEMOTO4Faculty of Science & Technology, Tokyo University of ScienceFaculty of Science & Technology, Tokyo University of ScienceFaculty of Science & Technology, Tokyo University of ScienceFaculty of Science & Technology, Tokyo University of ScienceFaculty of Science & Technology, Tokyo University of ScienceIn this study, the projected density of states (PDOS) of the stable normal-spinel structure and stable Mg/Co mixed-cation spinel structure of Mg1+yCo2−xMnxO4 (x = 0, 0.5; y = 0, 0.5, 1) in the pristine and discharged states are obtained using first-principles calculations. The spin state and the valence state of the transition metals are investigated. The overlaps of the d orbitals of the transition metals and the p orbitals of oxygen are large, and the covalency between the transition metal and oxygen is strong in the pristine MgCo2O4 and MgCo1.5Mn0.5O4. The M–O6 (M = Co, Mn) octahedra become stable as a host structure. From the PDOS spectra, Co atoms are in the trivalent low-spin state in pristine MgCo2O4 and MgCo1.5Mn0.5O4 and Mn atoms are nearly tetravalent in pristine MgCo1.5Mn0.5O4. In the discharge process, the overlap of the d orbitals of the transition metals and the p orbitals of oxygen becomes narrow and the valence of the transition metals decreases with increasing Mg insertion. The results of the first-principles calculations are consistent with those of X-ray absorption near edge structure spectra.https://www.jstage.jst.go.jp/article/electrochemistry/89/3/89_21-00024/_pdf/-char/enmagnesium secondary batterycathodefirst-principle calculationdensity of states |
| spellingShingle | Chiaki ISHIBASHI Mai ICHIYAMA Naoya ISHIDA Naoto KITAMURA Yasushi IDEMOTO Theoretical Study Using First-Principles Calculations of the Electronic Structures of Magnesium Secondary Battery Cathode Materials MgCo2−xMnxO4 (x = 0, 0.5) in the Pristine and Discharged States Electrochemistry magnesium secondary battery cathode first-principle calculation density of states |
| title | Theoretical Study Using First-Principles Calculations of the Electronic Structures of Magnesium Secondary Battery Cathode Materials MgCo2−xMnxO4 (x = 0, 0.5) in the Pristine and Discharged States |
| title_full | Theoretical Study Using First-Principles Calculations of the Electronic Structures of Magnesium Secondary Battery Cathode Materials MgCo2−xMnxO4 (x = 0, 0.5) in the Pristine and Discharged States |
| title_fullStr | Theoretical Study Using First-Principles Calculations of the Electronic Structures of Magnesium Secondary Battery Cathode Materials MgCo2−xMnxO4 (x = 0, 0.5) in the Pristine and Discharged States |
| title_full_unstemmed | Theoretical Study Using First-Principles Calculations of the Electronic Structures of Magnesium Secondary Battery Cathode Materials MgCo2−xMnxO4 (x = 0, 0.5) in the Pristine and Discharged States |
| title_short | Theoretical Study Using First-Principles Calculations of the Electronic Structures of Magnesium Secondary Battery Cathode Materials MgCo2−xMnxO4 (x = 0, 0.5) in the Pristine and Discharged States |
| title_sort | theoretical study using first principles calculations of the electronic structures of magnesium secondary battery cathode materials mgco2 xmnxo4 x 0 0 5 in the pristine and discharged states |
| topic | magnesium secondary battery cathode first-principle calculation density of states |
| url | https://www.jstage.jst.go.jp/article/electrochemistry/89/3/89_21-00024/_pdf/-char/en |
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