A novel P3-type Na                         2/3                         Mg                         1/3                         Mn                         2/3                         O                         2                          as high capacity sodium-ion cathode using reversible oxygen redox

Bohang Song; Enyuan Hu; Jue Liu; Yiman Zhang; Xiao Qing Yang; Jagjit Nanda; Ashfia Huq; Katharine Page

doi:10.1039/c8ta09422e

A novel P3-type Na _2/3 Mg _1/3 Mn _2/3 O ₂ as high capacity sodium-ion cathode using reversible oxygen redox

Bohang Song, Enyuan Hu, Jue Liu, Yiman Zhang, Xiao Qing Yang, Jagjit Nanda, Ashfia Huq, Katharine Page

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Research output: Contribution to journal › Article › peer-review

132 Scopus citations

Abstract

There is great interest in the discovery of Li/Na-ion cathode materials with capacity exceeding the limitation of conventional intercalation-based oxide cathodes. One plausible but challenging path is to reversibly use the charge compensation of both lattice oxygen redox and transition metal (TM) redox. Here, we report that lattice oxygen redox alone contributes over 190 mA h g ^-1 charge capacity (cut-off at 4.65 V vs. Na ⁺ /Na) for the newly synthesized P3-type Na _2/3 Mg _1/3 Mn(iv) _2/3 O ₂ . Similar amounts of discharge capacity are reversibly achieved. The discharge capacity exceeds 220 mA h g ^-1 when Mn ³⁺ /Mn ⁴⁺ redox is partially used in addition to the oxygen redox reaction. This represents one of the highest energy density sodium-ion cathodes with superior low-cost. Our results reveal that cations with strong ionic bonding nature with oxygen (such as Mg ²⁺ ) are very effective in inducing the reversible oxygen redox reaction. We also identified the origin of voltage hysteresis to be a P3-to-O3 phase transition in concomitance with Mg ²⁺ migration, suggesting further structure design that reduces the structure transition induced cation migration is critical for increasing the energy efficiency of the oxygen redox reactions.

Original language	English
Pages (from-to)	1491-1498
Number of pages	8
Journal	Journal of Materials Chemistry A
Volume	7
Issue number	4
DOIs	https://doi.org/10.1039/c8ta09422e
State	Published - 2019

Funding

This research is primarily supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Early Career Research Program award KC040602, under contract number DE-AC05-00OR22725. Research conducted at the NOMAD beamline at ORNL's Spallation Neutron Source was sponsored by the Scientic User Facilities Division, Office of Basic Sciences, U.S. Department of Energy. Research at the 11-ID-B and 11-BM beamlines used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research used resources at 7-BM 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. Enyuan Hu and Xiao-Qing Yang at Brookhaven National Laboratory were supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office of the U.S. DOE through the Advanced Battery Materials Research (BMR) Program, including Battery500 consortium under Contract DE-SC0012704. We would also like to thank Dr Nancy Dudney and Dr Craig Bridges for fruitful discussion and technical review. This research is primarily supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Early Career Research Program award KC040602, under contract number DE-AC05-00OR22725. Research conducted at the NOMAD beamline at ORNL's Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Sciences, U.S. Department of Energy. Research at the 11-ID-B and 11-BM beamlines used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research used resources at 7-BM 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. Enyuan Hu and Xiao-Qing Yang at Brookhaven National Laboratory were supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office of the U.S. DOE through the Advanced Battery Materials Research (BMR) Program, including Battery500 consortium under Contract DE-SC0012704. We would also like to thank Dr Nancy Dudney and Dr Craig Bridges for fruitful discussion and technical review.

Funders	Funder number
DOE Office of Science
Office of Basic Energy Sciences	DE-AC05-00OR22725, KC040602
Office of Basic Sciences
Scientic User Facilities Division
U.S. Department of Energy
Office of Science
Office of Energy Efficiency and Renewable Energy	DE-SC0012704
Argonne National Laboratory	DE-AC02-06CH11357
Brookhaven National Laboratory

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Cite this

Song, B., Hu, E., Liu, J., Zhang, Y., Yang, X. Q., Nanda, J., Huq, A., & Page, K. (2019). A novel P3-type Na _2/3 Mg _1/3 Mn _2/3 O ₂ as high capacity sodium-ion cathode using reversible oxygen redox Journal of Materials Chemistry A, 7(4), 1491-1498. https://doi.org/10.1039/c8ta09422e

Song, Bohang ; Hu, Enyuan ; Liu, Jue et al. / A novel P3-type Na _2/3 Mg _1/3 Mn _2/3 O ₂ as high capacity sodium-ion cathode using reversible oxygen redox In: Journal of Materials Chemistry A. 2019 ; Vol. 7, No. 4. pp. 1491-1498.

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abstract = " There is great interest in the discovery of Li/Na-ion cathode materials with capacity exceeding the limitation of conventional intercalation-based oxide cathodes. One plausible but challenging path is to reversibly use the charge compensation of both lattice oxygen redox and transition metal (TM) redox. Here, we report that lattice oxygen redox alone contributes over 190 mA h g -1 charge capacity (cut-off at 4.65 V vs. Na + /Na) for the newly synthesized P3-type Na 2/3 Mg 1/3 Mn(iv) 2/3 O 2 . Similar amounts of discharge capacity are reversibly achieved. The discharge capacity exceeds 220 mA h g -1 when Mn 3+ /Mn 4+ redox is partially used in addition to the oxygen redox reaction. This represents one of the highest energy density sodium-ion cathodes with superior low-cost. Our results reveal that cations with strong ionic bonding nature with oxygen (such as Mg 2+ ) are very effective in inducing the reversible oxygen redox reaction. We also identified the origin of voltage hysteresis to be a P3-to-O3 phase transition in concomitance with Mg 2+ migration, suggesting further structure design that reduces the structure transition induced cation migration is critical for increasing the energy efficiency of the oxygen redox reactions.",

author = "Bohang Song and Enyuan Hu and Jue Liu and Yiman Zhang and Yang, {Xiao Qing} and Jagjit Nanda and Ashfia Huq and Katharine Page",

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Song, B, Hu, E, Liu, J, Zhang, Y, Yang, XQ, Nanda, J, Huq, A & Page, K 2019, ' A novel P3-type Na _2/3 Mg _1/3 Mn _2/3 O ₂ as high capacity sodium-ion cathode using reversible oxygen redox ', Journal of Materials Chemistry A, vol. 7, no. 4, pp. 1491-1498. https://doi.org/10.1039/c8ta09422e

A novel P3-type Na _2/3 Mg _1/3 Mn _2/3 O ₂ as high capacity sodium-ion cathode using reversible oxygen redox . / Song, Bohang; Hu, Enyuan; Liu, Jue et al.
In: Journal of Materials Chemistry A, Vol. 7, No. 4, 2019, p. 1491-1498.

Research output: Contribution to journal › Article › peer-review

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AU - Yang, Xiao Qing

AU - Nanda, Jagjit

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AU - Page, Katharine

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AB - There is great interest in the discovery of Li/Na-ion cathode materials with capacity exceeding the limitation of conventional intercalation-based oxide cathodes. One plausible but challenging path is to reversibly use the charge compensation of both lattice oxygen redox and transition metal (TM) redox. Here, we report that lattice oxygen redox alone contributes over 190 mA h g -1 charge capacity (cut-off at 4.65 V vs. Na + /Na) for the newly synthesized P3-type Na 2/3 Mg 1/3 Mn(iv) 2/3 O 2 . Similar amounts of discharge capacity are reversibly achieved. The discharge capacity exceeds 220 mA h g -1 when Mn 3+ /Mn 4+ redox is partially used in addition to the oxygen redox reaction. This represents one of the highest energy density sodium-ion cathodes with superior low-cost. Our results reveal that cations with strong ionic bonding nature with oxygen (such as Mg 2+ ) are very effective in inducing the reversible oxygen redox reaction. We also identified the origin of voltage hysteresis to be a P3-to-O3 phase transition in concomitance with Mg 2+ migration, suggesting further structure design that reduces the structure transition induced cation migration is critical for increasing the energy efficiency of the oxygen redox reactions.

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Song B, Hu E, Liu J, Zhang Y, Yang XQ, Nanda J et al. A novel P3-type Na _2/3 Mg _1/3 Mn _2/3 O ₂ as high capacity sodium-ion cathode using reversible oxygen redox Journal of Materials Chemistry A. 2019;7(4):1491-1498. doi: 10.1039/c8ta09422e