Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state

Xuelong Wang, Liang Yin, Arthur Ronne, Yiman Zhang, Zilin Hu, Sha Tan, Qinchao Wang, Bohang Song, Mengya Li, Xiaohui Rong, Saul Lapidus, Shize Yang, Enyuan Hu () and Jue Liu ()
Additional contact information
Xuelong Wang: Brookhaven National Laboratory
Liang Yin: Chinese Academy of Sciences
Arthur Ronne: Brookhaven National Laboratory
Yiman Zhang: Oak Ridge National Laboratory
Zilin Hu: Chinese Academy of Sciences
Sha Tan: Brookhaven National Laboratory
Qinchao Wang: Brookhaven National Laboratory
Bohang Song: Oak Ridge National Laboratory
Mengya Li: Oak Ridge National Laboratory
Xiaohui Rong: Chinese Academy of Sciences
Saul Lapidus: Argonne National Laboratory
Shize Yang: Yale University
Enyuan Hu: Brookhaven National Laboratory
Jue Liu: Oak Ridge National Laboratory

Nature Communications, 2023, vol. 14, issue 1, 1-13

Abstract: Abstract Reversible lattice oxygen redox reactions offer the potential to enhance energy density and lower battery cathode costs. However, their widespread adoption faces obstacles like substantial voltage hysteresis and poor stability. The current research addresses these challenges by achieving a non-hysteresis, long-term stable oxygen redox reaction in the P3-type Na2/3Cu1/3Mn2/3O2. Here we show this is accomplished by forming spin singlet states during charge and discharge. Detailed analysis, including in-situ X-ray diffraction, shows highly reversible structural changes during cycling. In addition, local CuO6 Jahn-Teller distortions persist throughout, with dynamic Cu-O bond length variations. In-situ hard X-ray absorption and ex-situ soft X-ray absorption study, along with density function theory calculations, reveal two distinct charge compensation mechanisms at approximately 3.66 V and 3.99 V plateaus. Notably, we observe a Zhang-Rice-like singlet state during 3.99 V charging, offering an alternative charge compensation mechanism to stabilize the active oxygen redox reaction.

Date: 2023
References: View references in EconPapers View complete reference list from CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-023-43031-6 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-43031-6

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-023-43031-6

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().