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Title: A novel P3-type Na2/3Mg1/3Mn2/3O2 as high capacity sodium-ion cathode using reversible oxygen redox

Journal Article · · Journal of Materials Chemistry. A
DOI: https://doi.org/10.1039/C8TA09422E · OSTI ID:1485260
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)
+ Show Author Affiliations

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.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704; KC040602; AC05-00OR22725; AC02-06CH11357
OSTI ID:
1485260
Alternate ID(s):
OSTI ID: 1485332; OSTI ID: 1502593
Report Number(s):
BNL-209657-2018-JAAM; JMCAET
Journal Information:
Journal of Materials Chemistry. A, Vol. 7, Issue 4; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 104 works
Citation information provided by
Web of Science

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Understanding Challenges of Cathode Materials for Sodium‐Ion Batteries using Synchrotron‐Based X‐Ray Absorption Spectroscopy journal July 2019
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