X-ray absorption measurements on nickel cathode of sodium-beta alumina batteries: Fe-Ni-Cl chemical associations

Mark E. Bowden; Kyle J. Alvine; John L. Fulton; John P. Lemmon; Xiaochuan Lu; Bobbie Jo Webb-Robertson; Steve M. Heald; Mahalingam Balasubramanian; Devon R. Mortensen; Gerald T. Seidler; Nancy J. Hess

doi:10.1016/j.jpowsour.2013.08.046

X-ray absorption measurements on nickel cathode of sodium-beta alumina batteries: Fe-Ni-Cl chemical associations

Mark E. Bowden, Kyle J. Alvine, John L. Fulton, John P. Lemmon, Xiaochuan Lu, Bobbie Jo Webb-Robertson, Steve M. Heald, Mahalingam Balasubramanian, Devon R. Mortensen, Gerald T. Seidler, Nancy J. Hess

Emerging and Solid-State Batteries

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13 Scopus citations

Abstract

Sections of Na-Al-NiCl₂ cathodes from sodium-beta alumina ZEBRA batteries have been characterized with X-ray fluorescence mapping, and XANES measurements to probe the microstructure, elemental correlation, and chemical speciation after voltage cycling. Cycling was performed under identical load conditions at either 240 or 280 C operating temperature and subsequently quenched in either the charged or discharged state. X-ray fluorescence mapping and XANES measurements were made adjacent to the current collector and β″-Al₂O₃ solid electrolyte interfaces to detect possible gradients in chemical properties across the cathode. An FeS additive, introduced during battery synthesis, was found to be present as either Fe metal or an Fe(II) chloride in all cathode samples. X-ray fluorescence mapping reveals an operating temperature and charge-state dependent spatial correlation between Fe, Ni, and Cl concentration. XANES measurements indicate that both Ni and Fe are chemically reactive and shift between metallic and chloride phases in the charged and discharged states, respectively. However the percentage of chemically active Ni and Fe is significantly less in the cell operated at lower temperature. Additionally, the cathode appeared chemically homogeneous at the scale of our X-ray measurements.

Original language	English
Pages (from-to)	517-526
Number of pages	10
Journal	Journal of Power Sources
Volume	247
DOIs	https://doi.org/10.1016/j.jpowsour.2013.08.046
State	Published - 2014

Funding

The authors thank Drs. G. Coffey and A.L. Schemer-Kohrn for synthesis of the cathode samples and SEM/EDS analysis. Research was performed at the Pacific Northwest National Laboratory (PNNL) managed under DOE contract No. DE-AC05-76RL01830. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357 . The authors gratefully acknowledge Laboratory Directed Research and Development (LDRD) project funding from the PNNL Chemical Imaging Initiative .

Keywords

Chemical mapping
Fe additives
Sodium-nickel chloride battery
X-ray absorption spectroscopy

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10.1016/j.jpowsour.2013.08.046

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Bowden, M. E., Alvine, K. J., Fulton, J. L., Lemmon, J. P., Lu, X., Webb-Robertson, B. J., Heald, S. M., Balasubramanian, M., Mortensen, D. R., Seidler, G. T., & Hess, N. J. (2014). X-ray absorption measurements on nickel cathode of sodium-beta alumina batteries: Fe-Ni-Cl chemical associations. Journal of Power Sources, 247, 517-526. https://doi.org/10.1016/j.jpowsour.2013.08.046

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title = "X-ray absorption measurements on nickel cathode of sodium-beta alumina batteries: Fe-Ni-Cl chemical associations",

abstract = "Sections of Na-Al-NiCl2 cathodes from sodium-beta alumina ZEBRA batteries have been characterized with X-ray fluorescence mapping, and XANES measurements to probe the microstructure, elemental correlation, and chemical speciation after voltage cycling. Cycling was performed under identical load conditions at either 240 or 280 C operating temperature and subsequently quenched in either the charged or discharged state. X-ray fluorescence mapping and XANES measurements were made adjacent to the current collector and β″-Al2O3 solid electrolyte interfaces to detect possible gradients in chemical properties across the cathode. An FeS additive, introduced during battery synthesis, was found to be present as either Fe metal or an Fe(II) chloride in all cathode samples. X-ray fluorescence mapping reveals an operating temperature and charge-state dependent spatial correlation between Fe, Ni, and Cl concentration. XANES measurements indicate that both Ni and Fe are chemically reactive and shift between metallic and chloride phases in the charged and discharged states, respectively. However the percentage of chemically active Ni and Fe is significantly less in the cell operated at lower temperature. Additionally, the cathode appeared chemically homogeneous at the scale of our X-ray measurements.",

keywords = "Chemical mapping, Fe additives, Sodium-nickel chloride battery, X-ray absorption spectroscopy",

author = "Bowden, {Mark E.} and Alvine, {Kyle J.} and Fulton, {John L.} and Lemmon, {John P.} and Xiaochuan Lu and Webb-Robertson, {Bobbie Jo} and Heald, {Steve M.} and Mahalingam Balasubramanian and Mortensen, {Devon R.} and Seidler, {Gerald T.} and Hess, {Nancy J.}",

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doi = "10.1016/j.jpowsour.2013.08.046",

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pages = "517--526",

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AU - Bowden, Mark E.

AU - Alvine, Kyle J.

AU - Fulton, John L.

AU - Lemmon, John P.

AU - Lu, Xiaochuan

AU - Webb-Robertson, Bobbie Jo

AU - Heald, Steve M.

AU - Balasubramanian, Mahalingam

AU - Mortensen, Devon R.

AU - Seidler, Gerald T.

AU - Hess, Nancy J.

PY - 2014

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N2 - Sections of Na-Al-NiCl2 cathodes from sodium-beta alumina ZEBRA batteries have been characterized with X-ray fluorescence mapping, and XANES measurements to probe the microstructure, elemental correlation, and chemical speciation after voltage cycling. Cycling was performed under identical load conditions at either 240 or 280 C operating temperature and subsequently quenched in either the charged or discharged state. X-ray fluorescence mapping and XANES measurements were made adjacent to the current collector and β″-Al2O3 solid electrolyte interfaces to detect possible gradients in chemical properties across the cathode. An FeS additive, introduced during battery synthesis, was found to be present as either Fe metal or an Fe(II) chloride in all cathode samples. X-ray fluorescence mapping reveals an operating temperature and charge-state dependent spatial correlation between Fe, Ni, and Cl concentration. XANES measurements indicate that both Ni and Fe are chemically reactive and shift between metallic and chloride phases in the charged and discharged states, respectively. However the percentage of chemically active Ni and Fe is significantly less in the cell operated at lower temperature. Additionally, the cathode appeared chemically homogeneous at the scale of our X-ray measurements.

AB - Sections of Na-Al-NiCl2 cathodes from sodium-beta alumina ZEBRA batteries have been characterized with X-ray fluorescence mapping, and XANES measurements to probe the microstructure, elemental correlation, and chemical speciation after voltage cycling. Cycling was performed under identical load conditions at either 240 or 280 C operating temperature and subsequently quenched in either the charged or discharged state. X-ray fluorescence mapping and XANES measurements were made adjacent to the current collector and β″-Al2O3 solid electrolyte interfaces to detect possible gradients in chemical properties across the cathode. An FeS additive, introduced during battery synthesis, was found to be present as either Fe metal or an Fe(II) chloride in all cathode samples. X-ray fluorescence mapping reveals an operating temperature and charge-state dependent spatial correlation between Fe, Ni, and Cl concentration. XANES measurements indicate that both Ni and Fe are chemically reactive and shift between metallic and chloride phases in the charged and discharged states, respectively. However the percentage of chemically active Ni and Fe is significantly less in the cell operated at lower temperature. Additionally, the cathode appeared chemically homogeneous at the scale of our X-ray measurements.

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X-ray absorption measurements on nickel cathode of sodium-beta alumina batteries: Fe-Ni-Cl chemical associations

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