Browsing by Author "Cabana, J"

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    Designing novel tunable Mn-based inorganic oxyfluoride pigments
    (Elsevier, 2024-06) Lehr, B; Zurowski, G; Chhoeun, J; Kumar, K; Nolis, G; Shanahan, J; Kilpatrick, K; Rojas, K; Cabana, J; Kissel, D; Avdeev, M; Sullivan, E
    A high tunability of green-blue colors in the manganese-doped oxyfluoride Sr2.5A0.5Mn0.1MO4F (A = Ca, Sr, Ba; M = Al, Ga) and anion-deficient Sr2.5A0.5Mn0.1MO4-αF1-δ (A = Ca, Sr, Ba; M = Al, Ga) is reported, and the chromophores responsible for this intense pigmentation are investigated. The hues exhibited by these materials are quantified via diffuse reflectance UV/Vis spectroscopy and measurement of their direct band gaps via Tauc plot. It is shown that choice of A cation (A = Ca, Sr, Ba) and M cation (M = Al, Ga) for as-synthesized phases Sr2.5A0.5Mn0.1MO4F yield a wide range of green colors (band gap range 2.70–2.96 eV). Treatment of these phases under reducing conditions according to Sr2.5A0.5Mn0.1MO4-αF1-δ (A = Ca, Sr, Ba; M = Al, Ga) induces anion non-stoichiometry, shifting the observed colors to a wide range of blue/blue-purple hues (band gaps from 3.31 to 3.66 eV), showing potential as tunable inorganic blue pigments. Density field theory (DFT) calculations support the preferential occupation of the smaller 8-coordinate Sr(2) site by the substituted Mn2+ cation. X-ray absorption near-edge structure (XANES) data reveal more subtle nuances in the interplay between formal manganese oxidation state, crystallographic site and observed hue. In general, for as synthesized (green) Sr2.5A0.5Mn0.1MO4F (A = Ca, Sr, Ba; M = Al, Ga), the edge position in Mn K-edge XANES is consistent with mixed Mn3+-Mn4+ oxidation state whilst a clear pre-edge structure suggesting that Mn is present on a tetrahedral site. This would suggest that during the reduction step, Mn3+/Mn4+ is reduced to entirely Mn2+ and migrates from the tetrahedral to the Sr(2) lattice site. © 2024 Elsevier Ltd. All rights reserved.
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    Unlocking anionic redox activity in O3-type sodium 3d layered oxides via Li substitution
    (Springer Nature, 2021-01-11) lorem, Ipsum; Wang, Q; Mariyappan, S; Rousse, G; Morozov, AV; Porcheron, B; Dedryvère, R; Wu, JP; Yang, WL; Zhang, LT; Chakir, M; Avdeev, M; Deschamps, M; Yu, YS; Cabana, J; Doublet, ML; Abakumov, AM; Tarascon, JM
    Sodium ion batteries, because of their sustainability attributes, could be an attractive alternative to Li-ion technology for specific applications. However, it remains challenging to design high energy density and moisture stable Na-based positive electrodes. Here, we report an O3-type NaLi1/3Mn2/3O2 phase showing anionic redox activity, obtained through a ceramic process by carefully adjusting synthesis conditions and stoichiometry. This phase shows a sustained reversible capacity of 190 mAh g−1 that is rooted in cumulative oxygen and manganese redox processes as deduced by combined spectroscopy techniques. Unlike many other anionic redox layered oxides so far reported, O3-NaLi1/3Mn2/3O2 electrodes do not show discernible voltage fade on cycling. This finding, rationalized by density functional theory, sheds light on the role of inter- versus intralayer 3d cationic migration in ruling voltage fade in anionic redox electrodes. Another practical asset of this material stems from its moisture stability, hence facilitating its handling and electrode processing. Overall, this work offers future directions towards designing highly performing sodium electrodes for advanced Na-ion batteries. © 2021, The Author(s), under exclusive licence to Springer Nature Limited.