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Stabilizing Transition Metal Vacancy Induced Oxygen Redox by Co2+/Co3+ Redox and Sodium-Site Doping for Layered Cathode Materials

Journal Article · · Angewandte Chemie (International Edition)
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  1. Fudan Univ., Shanghai (China)
  2. Shanghai Jiao Tong Univ. (China)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

Anionic redox is an effective way to boost the energy density of layer-structured metal-oxide cathodes for rechargeable batteries. However, inherent rigid nature of the TMO6 (TM: transition metals) subunits in the layered materials makes it hardly tolerate the inner strains induced by lattice glide, especially at high voltage. Herein, P2-Na0.8Mg0.13[Mn0.6Co0.2Mg0.07$$\square$$0.13]O2 ($$\square$$: TM vacancy) is designed that contains vacancies in TM sites, and Mg ions in both TM and sodium sites. Vacancies make the rigid TMO6 octahedron become more asymmetric and flexible. Low valence Co2+/Co3+ redox couple stabilizes the electronic structure, especially at the charged state. Mg2+ in sodium sites can tune the interlayer spacing against O-O electrostatic repulsion. Time-resolved in situ X-ray diffraction confirms that irreversible structure evolution is effectively suppressed during deep desodiation benefiting from the specific configuration. X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations demonstrate that, deriving from the intrinsic vacancies, multiple local configurations of “$$\square$$-O-$$\square$$”, “Na-O-$$\square$$”, “Mg-O-$$\square$$” are superior in facilitating the oxygen redox for charge compensation than previously reported “Na-O-Mg”. The resulted material delivers promising cycle stability and rate capability, with a long voltage plateau at 4.2 V contributed by oxygen, and can be well maintained even at high rates. The strategy will inspire new ideas in designing highly stable cathode materials with reversible anionic redox for sodium-ion batteries.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; National Natural Science Foundation of China (NSFC); Science & Technology Commission of Shanghai Municipality; National Key R&D Program of China; China Postdoctoral Science Foundation; Zhuhai Fudan Innovation Institute
Grant/Contract Number:
SC0012704
OSTI ID:
1820169
Report Number(s):
BNL--222094-2021-JAAM
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 40 Vol. 60; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
cathode materials
intrinsic vacancies
oxygen redox
sodium sites
sodium-ion batteries