Direct Mechanochemical Synthesis, Phase Stability, and Electrochemical Performance of α-NaFeO2

Rebecca D. McAuliffe; Gabrielle E. Kamm; Matthew J. McDermott; Raphaël P. Hermann; Neyanel Vasquez-Garcia; Robert L. Sacci; Kristin A. Persson; Karena W. Chapman; Gabriel M. Veith

doi:10.1021/acs.inorgchem.2c03286

Direct Mechanochemical Synthesis, Phase Stability, and Electrochemical Performance of α-NaFeO₂

Rebecca D. McAuliffe, Gabrielle E. Kamm, Matthew J. McDermott, Raphaël P. Hermann, Neyanel Vasquez-Garcia, Robert L. Sacci, Kristin A. Persson, Karena W. Chapman, Gabriel M. Veith

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Abstract

To better understand polymorph control in transition metal oxides, the mechanochemical synthesis of NaFeO₂ was explored. Herein, we report the direct synthesis of α-NaFeO₂ through a mechanochemical process. By milling Na₂O₂ and γ-Fe₂O₃ for 5 h, α-NaFeO₂ was prepared without high-temperature annealing needed in other synthesis methods. While investigating the mechanochemical synthesis, it was observed that changing the starting precursors and mass of precursors affects the resulting NaFeO₂ structure. Density functional theory calculations on the phase stability of NaFeO₂ phases show that the α phase is stabilized over the β phase in oxidizing environments, which is provided by the oxygen-rich reaction between Na₂O₂ and Fe₂O₃. This provides a possible route to understanding polymorph control in NaFeO₂. Annealing the as-milled α-NaFeO₂ at 700 °C has resulted in increased crystallinity and structural changes that improved electrochemical performance in terms of capacity over the as-milled sample.

Original language	English
Pages (from-to)	3358-3367
Number of pages	10
Journal	Inorganic Chemistry
Volume	62
Issue number	8
DOIs	https://doi.org/10.1021/acs.inorgchem.2c03286
State	Published - Feb 27 2023

Funding

This work was supported as part of GENESIS: A Next Generation Synthesis Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DE-SC0019212. The work of G.E.K. was in part supported as a part of QuADS: Quantitative Analysis of Dynamic Structures National Science Foundation Research Traineeship Program, grant number NSF DGE 1922639. TGA measurements were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering. Research was performed at Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U.S. Department of Energy (DOE) under Contract DE-AC05-00OR22725. This research used resources at the 28-ID-1 beamline of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Calculations performed in this research used resources of the National Energy Research Scientific Computing Center (NERSC) under Award Number BES-ERCAP0020225, a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under Contract No. DE-AC02-05CH11231. Mössbauer spectroscopy was supported by the US DOE Office of Science, Basic Energy Science, Materials Science and Engineering Division. The authors would like to thank Nicholas Winner for helpful discussion regarding the analysis of defect thermodynamics. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Acknowledgments

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title = "Direct Mechanochemical Synthesis, Phase Stability, and Electrochemical Performance of α-NaFeO2",

abstract = "To better understand polymorph control in transition metal oxides, the mechanochemical synthesis of NaFeO2 was explored. Herein, we report the direct synthesis of α-NaFeO2 through a mechanochemical process. By milling Na2O2 and γ-Fe2O3 for 5 h, α-NaFeO2 was prepared without high-temperature annealing needed in other synthesis methods. While investigating the mechanochemical synthesis, it was observed that changing the starting precursors and mass of precursors affects the resulting NaFeO2 structure. Density functional theory calculations on the phase stability of NaFeO2 phases show that the α phase is stabilized over the β phase in oxidizing environments, which is provided by the oxygen-rich reaction between Na2O2 and Fe2O3. This provides a possible route to understanding polymorph control in NaFeO2. Annealing the as-milled α-NaFeO2 at 700 °C has resulted in increased crystallinity and structural changes that improved electrochemical performance in terms of capacity over the as-milled sample.",

author = "McAuliffe, {Rebecca D.} and Kamm, {Gabrielle E.} and McDermott, {Matthew J.} and Hermann, {Rapha{\"e}l P.} and Neyanel Vasquez-Garcia and Sacci, {Robert L.} and Persson, {Kristin A.} and Chapman, {Karena W.} and Veith, {Gabriel M.}",

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year = "2023",

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day = "27",

doi = "10.1021/acs.inorgchem.2c03286",

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AU - McAuliffe, Rebecca D.

AU - Kamm, Gabrielle E.

AU - McDermott, Matthew J.

AU - Hermann, Raphaël P.

AU - Vasquez-Garcia, Neyanel

AU - Sacci, Robert L.

AU - Persson, Kristin A.

AU - Chapman, Karena W.

AU - Veith, Gabriel M.

PY - 2023/2/27

Y1 - 2023/2/27

N2 - To better understand polymorph control in transition metal oxides, the mechanochemical synthesis of NaFeO2 was explored. Herein, we report the direct synthesis of α-NaFeO2 through a mechanochemical process. By milling Na2O2 and γ-Fe2O3 for 5 h, α-NaFeO2 was prepared without high-temperature annealing needed in other synthesis methods. While investigating the mechanochemical synthesis, it was observed that changing the starting precursors and mass of precursors affects the resulting NaFeO2 structure. Density functional theory calculations on the phase stability of NaFeO2 phases show that the α phase is stabilized over the β phase in oxidizing environments, which is provided by the oxygen-rich reaction between Na2O2 and Fe2O3. This provides a possible route to understanding polymorph control in NaFeO2. Annealing the as-milled α-NaFeO2 at 700 °C has resulted in increased crystallinity and structural changes that improved electrochemical performance in terms of capacity over the as-milled sample.

AB - To better understand polymorph control in transition metal oxides, the mechanochemical synthesis of NaFeO2 was explored. Herein, we report the direct synthesis of α-NaFeO2 through a mechanochemical process. By milling Na2O2 and γ-Fe2O3 for 5 h, α-NaFeO2 was prepared without high-temperature annealing needed in other synthesis methods. While investigating the mechanochemical synthesis, it was observed that changing the starting precursors and mass of precursors affects the resulting NaFeO2 structure. Density functional theory calculations on the phase stability of NaFeO2 phases show that the α phase is stabilized over the β phase in oxidizing environments, which is provided by the oxygen-rich reaction between Na2O2 and Fe2O3. This provides a possible route to understanding polymorph control in NaFeO2. Annealing the as-milled α-NaFeO2 at 700 °C has resulted in increased crystallinity and structural changes that improved electrochemical performance in terms of capacity over the as-milled sample.

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JF - Inorganic Chemistry

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Direct Mechanochemical Synthesis, Phase Stability, and Electrochemical Performance of α-NaFeO₂

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