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K-Doping Suppresses Oxygen Redox in P2-Na₀.₆₇Ni₀.₁₁Cu₀.₂₂Mn₀.₆₇O₂ Cathode Materials for Sodium-Ion Batteries

Title data

Zhou, Bei ; Wong, Deniz ; Fu, Zhongheng ; Guo, Hao ; Schulz, Christian ; Karkera, Guruprakash ; Hahn, Horst ; Bianchini, Matteo ; Wang, Qingsong:
K-Doping Suppresses Oxygen Redox in P2-Na₀.₆₇Ni₀.₁₁Cu₀.₂₂Mn₀.₆₇O₂ Cathode Materials for Sodium-Ion Batteries.
In: Small. (3 July 2024) . - 2402991.
ISSN 1613-6829
DOI: https://doi.org/10.1002/smll.202402991

Official URL: Volltext

Abstract in another language

Abstract In P2-type layered oxide cathodes, Na site-regulation strategies are proposed to modulate the Na+ distribution and structural stability. However, their impact on the oxygen redox reactions remains poorly understood. Herein, the incorporation of K+ in the Na layer of Na0.67Ni0.11Cu0.22Mn0.67O2 is successfully applied. The effects of partial substitution of Na+ with K+ on electrochemical properties, structural stability, and oxygen redox reactions have been extensively studied. Improved Na+ diffusion kinetics of the cathode is observed from galvanostatic intermittent titration technique (GITT) and rate performance. The valence states and local structural environment of the transition metals (TMs) are elucidated via operando synchrotron X-ray absorption spectroscopy (XAS). It is revealed that the TMO2 slabs tend to be strengthened by K-doping, which efficiently facilitates reversible local structural change. Operando X-ray diffraction (XRD) further confirms more reversible phase changes during the charge/discharge for the cathode after K-doping. Density functional theory (DFT) calculations suggest that oxygen redox reaction in Na0.62K0.03Ni0.11Cu0.22Mn0.67O2 cathode has been remarkably suppressed as the nonbonding O 2p states shift down in the energy. This is further corroborated experimentally by resonant inelastic X-ray scattering (RIXS) spectroscopy, ultimately proving the role of K+ incorporated in the Na layer.

Further data

Item Type: Article in a journal
Refereed: Yes
Keywords: K-doping; Oxygen redox reactions; P2-type cathodes; sodium-ion batteries
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Lehrstuhl Anorganische Aktivmaterialien für elektrochemische Energiespeicher
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Lehrstuhl Anorganische Aktivmaterialien für elektrochemische Energiespeicher > Lehrstuhl Anorganische Aktivmaterialien für elektrochemische Energiespeicher - Univ.-Prof. Dr. Matteo Bianchini
Research Institutions > Central research institutes > Bayerisches Zentrum für Batterietechnik - BayBatt
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Research Institutions
Research Institutions > Central research institutes
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 500 Natural sciences
500 Science > 540 Chemistry
Date Deposited: 04 Jul 2024 08:48
Last Modified: 09 Jul 2024 10:40
URI: https://eref.uni-bayreuth.de/id/eprint/89900