(De)lithiation of spinel ferrites Fe3O4, MgFe2O4, and ZnFe2O4: a combined spectroscopic, diffraction and theory study
| Autor: | Shan Yan, Ping Liu, Alison H. McCarthy, Calvin D. Quilty, Andrea M. Bruck, Haoyue Guo, Bingjie Zhang, Diana M. Lutz, Veronica Burnett, Killian R. Tallman, David C. Bock, Esther S. Takeuchi, Paul F. Smith, Kenneth J. Takeuchi, Amy C. Marschilok, Matthew M. Huie |
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| Rok vydání: | 2020 |
| Předmět: |
Materials science
Absorption spectroscopy Spinel Iron oxide General Physics and Astronomy 02 engineering and technology engineering.material 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Ion chemistry.chemical_compound Crystallography Octahedron Transition metal chemistry engineering Density functional theory Physical and Theoretical Chemistry 0210 nano-technology Magnetite |
| Zdroj: | Physical Chemistry Chemical Physics. 22:26200-26215 |
| ISSN: | 1463-9084 1463-9076 |
| Popis: | Iron based materials hold promise as next generation battery electrode materials for Li ion batteries due to their earth abundance, low cost, and low environmental impact. The iron oxide, magnetite Fe3O4, adopts the spinel (AB2O4) structure. Other 2+ cation transition metal centers can also occupy both tetrahedral and/or octahedral sites in the spinel structure including MgFe2O4, a partially inverse spinel, and ZnFe2O4, a normal spinel. Though structurally similar to Fe3O4 in the pristine state, previous studies suggest significant differences in structural evolution depending on the 2+ cation in the structure. This investigation involves X-ray absorption spectroscopy and X-ray diffraction affirmed by density functional theory (DFT) to elucidate the role of the 2+ cation on the structural evolution and phase transformations during (de)lithiation of the spinel ferrites Fe3O4, MgFe2O4, and ZnFe2O4. The cation in the inverse, normal and partially inverse spinel structures located in the tetrahedral (8a) site migrates to the previously unoccupied octahedral 16c site by 2 electron equivalents of lithiation, resulting in a disordered [A]16c[B2]16dO4 structure. DFT calculations support the experimental results, predicting full displacement of the 8a cation to the 16c site at 2 electron equivalents. Substitution of the 2+ cation results in segregation of oxidized phases in the charged state. This report provides significant structural insight into the (de)lithiation mechanisms for an intriguing class of iron oxide materials. |
| Databáze: | OpenAIRE |
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