AI Article Synopsis
- Olivines are silicate minerals characterized by a specific structure where isolated silicon tetrahedra are linked through octahedra of different types.
- This study examines synthetic olivine crystals with up to 25% lithium-iron, revealing a clear ordering of lithium and iron in the crystal structure and suggesting that Li can effectively substitute for magnesium in olivine.
- Findings indicate that while certain structural distortions occur due to the weaker lithium-oxygen bonds, there is still a balance in the charge, pointing to the need for further research on lithium insertion for potential use in lithium-ion batteries.
Article Abstract
Olivines are naturally occurring silicates consisting of isolated (SiO) tetrahedra linked through 1O and 2O octahedra. In this study, we report the structural and crystal-chemical characterization of synthetic olivine crystals containing up to 25% Li-Fe synthesized using the flux growth technique. Based on site scattering, <1-O> and <2-O> mean bond lengths, and charge neutrality of the chemical formula, we found a perfect ordering of Li and Fe at the two distinct 1 and 2 sites. Unrestrained linear extrapolation to a hypothetical isostructural LiFe(SiO) composition aligns well with the tabulated ionic radii of Li and Fe. Comparison made with the isostructural LiSc(SiO) reveals that the Li-centered 2O octahedron has a significant capacity to distort in order to accommodate structural stresses, due to the relatively weak Li-O bond, while still achieving a bond valence sum that closely matches the formal charge of Li. This behavior suggests the potential feasibility of an extended Li + Fe for 2 Mg coupled substitution within the olivine structure. The reported structure of the LiFe(SiO) endmember in the literature, despite its apparent matching of cell dimensions and space group with olivine, exhibits extremely unconventional crystal chemical features, raising questions about its validity. Given the importance of the suitability of Li-insertion in LiFeSiO as electrodes in rechargeable Li-ion batteries, further studies are needed to investigate its crystal structure and crystal chemistry.
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| http://dx.doi.org/10.1021/acs.inorgchem.4c02611 | DOI Listing |
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