Electronic Structure and Properties of Lithium-Rich Complex Oxides

Hoang, Khang; Oh, Myungkeun; Choi, Yongki

doi:10.1021/acsaelm.8b00025

Cited by 14 publications

(10 citation statements)

References 40 publications

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“…For Li 5 FeO 4 and NaFeO 2 , no experimental band gap values are reported, to the best of our knowledge. Hoang et al [ 51 ] derived a band gap of 4.4 eV for Li 5 FeO 4 using hybrid-functional DFT calculations with nonoptimized mixing or screening parameters. This value is considerably larger than the DFT+ U results obtained here.…”

Section: Resultsmentioning

confidence: 99%

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

2020

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Knowledge about the formation energies of compounds is essential to derive phase diagrams of multicomponent phases with respect to elemental reservoirs. The determination of formation energies using common (semi-)local exchange-correlation approximations of the density functional theory (DFT) exhibits well-known systematic errors if applied to oxide compounds containing transition metal elements. In this work, we generalize, reevaluate, and discuss a set of approaches proposed and widely applied in the literature to correct for errors arising from the over-binding of the O2 molecule and from correlation effects of electrons in localized transition-metal orbitals. The DFT+U method is exemplarily applied to iron oxide compounds, and a procedure is presented to obtain the U values, which lead to formation energies and electronic band gaps comparable to the experimental values. Using such corrected formation energies, we derive the phase diagrams for LaFeO3, Li5FeO4, and NaFeO2, which are promising materials for energy conversion and storage devices. A scheme is presented to transform the variables of the phase diagrams from the chemical potentials of elemental phases to those of precursor compounds of a solid-state reaction, which represents the experimental synthesis process more appropriately. The discussed workflow of the methods can directly be applied to other transition metal oxides.

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Section: Resultsmentioning

confidence: 99%

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

2020

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“…Hoang et al [47] derived a band gap of 4.4 eV for Li5FeO4 using hybrid-functional DFT calculations with non-optimized mixing or screening parameters. This value is considerably larger than the DFT+U results obtained here.…”

Section: Band Gaps Of the Iron Compoundsmentioning

confidence: 99%

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

Mutter

Urban

Elsässer

2020

Preprint

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Knowledge about the formation energies of compounds is essential to derive phase diagrams of multi-component phases with respect to elemental reservoirs. The determination of formation energies using common (semi-)local exchange-correlation approximations of density functional theory (DFT) exhibits well-known systematic errors if applied to oxide compounds containing transition metal elements. In this work, we generalize, reevaluate and discuss a set of approaches proposed and widely applied in the literature to correct for errors arising from the over-binding of the O2 molecule and from correlation effects of electrons in localized transition-metal orbitals. The DFT+U method is exemplarily applied to iron oxide compounds, and a procedure is presented to obtain U values, which lead to formation energies and electronic band gaps comparable to experimental values. Using such corrected formation energies, we derive the phase diagrams for LaFeO3, Li5FeO4 and NaFeO2, which are promising materials for energy conversion and storage devices. A scheme is presented to transform the variables of the phase diagrams from the chemical potentials of elemental phases to those of precursor compounds of a solid-state reaction, which represents the experimental synthesis process more appropriately. The discussed workflow of methods can directly be applied to other transition metal oxides.

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“…52 Compounds such as Li 6 CoO 4 , Li 6 MnO 4 , and Li 5 FeO 4 are some of the previously studied Li-rich cathode materials with a defect anti-uorite structure. 45,[53][54][55][56][57][58][59][60][61][62] Among these compounds, Li 5 FeO 4 is found to be more attractive as a high-capacity cathode material exhibiting simultaneous anionic and cationic redox activity. Furthermore, the presence of abundantly available 3d Fe in place of 4d and 5d TMs such as Ru and Ir in common Li-rich materials 63,64 has a benecial impact on the molecular mass and the cost of the material.…”

Section: Introductionmentioning

confidence: 99%

Suppressing the initial capacity fade in Li-rich Li₅FeO₄with anionic redox by partial Co substitution – a first-principles study

Augustine

Sudarsanan

Ravindran

2023

Sustainable Energy Fuels

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Electronic Structure and Properties of Lithium-Rich Complex Oxides

Cited by 14 publications

References 40 publications

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

Suppressing the initial capacity fade in Li-rich Li₅FeO₄with anionic redox by partial Co substitution – a first-principles study

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Electronic Structure and Properties of Lithium-Rich Complex Oxides

Cited by 14 publications

References 40 publications

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

Determination of Formation Energies and Phase Diagrams of Transition Metal Oxides with DFT+U

Suppressing the initial capacity fade in Li-rich Li5FeO4with anionic redox by partial Co substitution – a first-principles study

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Suppressing the initial capacity fade in Li-rich Li₅FeO₄with anionic redox by partial Co substitution – a first-principles study