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Title: Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22 Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries

Journal Article · · Advanced Science
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  1. Department of Materials Science, Fudan University, Shanghai 200433 P. R. China
  2. Chemistry Division, Brookhaven National Laboratory, Upton NY 11973 USA
  3. Department of Chemistry & Laser Chemistry Institute, Fudan University, Shanghai 200433 P. R. China
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Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na0.66CoxMn0.66–xTi0.34O2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na0.66CoxMn0.66–xTi0.34O2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na0.66Co0.22Mn0.44Ti0.34O2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g-1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g-1 can still be obtained, indicating a promising rate capability. The low valence Co2+ substitution results in the formation of average Mn3.7+ valence state in Na0.66Co0.22Mn0.44Ti0.34O2, effectively suppressing the Mn3+-induced Jahn–Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na0.66Co0.22Mn0.44Ti0.34O2 during charge/discharge is contributed by Co2.2+/Co3+ and Mn3.3+/Mn4+ redox couples. This is the first time that the highly reversible Co2+/Co3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; SC0012704
OSTI ID:
1368103
Alternate ID(s):
OSTI ID: 1368104; OSTI ID: 1376159
Report Number(s):
BNL-114116-2017-JA; 1700219
Journal Information:
Advanced Science, Journal Name: Advanced Science; ISSN 2198-3844
Publisher:
WileyCopyright Statement
Country of Publication:
Germany
Language:
English
Citation Metrics:
Cited by: 83 works
Citation information provided by
Web of Science

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National Synchrotron Light Source