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

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 2/3Mg 1/3Mn(IV) 2/3O 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. Furthermore, 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.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Report Number(s):
BNL-209657-2018-JAAM
Journal ID: ISSN 2050-7488; JMCAET
Grant/Contract Number:
SC0012704; KC040602; AC05-00OR22725; AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Name: Journal of Materials Chemistry. A; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE
OSTI Identifier:
1485260
Alternate Identifier(s):
OSTI ID: 1485332

Song, Bohang, Hu, Enyuan, Liu, Jue, Zhang, Yiman, Yang, Xiao -Qing, Nanda, Jagjit, Huq, Ashfia, and Page, Katharine. A novel P3-type Na2/3Mg1/3Mn2/3O2 as high capacity sodium-ion cathode using reversible oxygen redox. United States: N. p., Web. doi:10.1039/C8TA09422E.
Song, Bohang, Hu, Enyuan, Liu, Jue, Zhang, Yiman, Yang, Xiao -Qing, Nanda, Jagjit, Huq, Ashfia, & Page, Katharine. A novel P3-type Na2/3Mg1/3Mn2/3O2 as high capacity sodium-ion cathode using reversible oxygen redox. United States. doi:10.1039/C8TA09422E.
Song, Bohang, Hu, Enyuan, Liu, Jue, Zhang, Yiman, Yang, Xiao -Qing, Nanda, Jagjit, Huq, Ashfia, and Page, Katharine. 2018. "A novel P3-type Na2/3Mg1/3Mn2/3O2 as high capacity sodium-ion cathode using reversible oxygen redox". United States. doi:10.1039/C8TA09422E.
@article{osti_1485260,
title = {A novel P3-type Na2/3Mg1/3Mn2/3O2 as high capacity sodium-ion cathode using reversible oxygen redox},
author = {Song, Bohang and Hu, Enyuan and Liu, Jue and Zhang, Yiman and Yang, Xiao -Qing and Nanda, Jagjit and Huq, Ashfia and Page, Katharine},
abstractNote = {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 Na2/3Mg1/3Mn(IV)2/3O2. Similar amounts of discharge capacity are reversibly achieved. The discharge capacity exceeds 220 mA h g–1 when Mn3+/Mn4+ 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 Mg2+) are very effective in inducing the reversible oxygen redox reaction. Furthermore, we also identified the origin of voltage hysteresis to be a P3-to-O3 phase transition in concomitance with Mg2+ 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.},
doi = {10.1039/C8TA09422E},
journal = {Journal of Materials Chemistry. A},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {12}
}

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