EconPapers    
Economics at your fingertips  
 

Transition metal migration and O2 formation underpin voltage hysteresis in oxygen-redox disordered rocksalt cathodes

Kit McColl, Robert A. House, Gregory J. Rees, Alexander G. Squires, Samuel W. Coles, Peter G. Bruce, Benjamin J. Morgan and M. Saiful Islam (saiful.islam@materials.ox.ac.uk)
Additional contact information
Kit McColl: University of Bath
Robert A. House: Harwell Science and Innovation Campus
Gregory J. Rees: Harwell Science and Innovation Campus
Alexander G. Squires: University of Bath
Samuel W. Coles: University of Bath
Peter G. Bruce: Harwell Science and Innovation Campus
Benjamin J. Morgan: University of Bath
M. Saiful Islam: University of Bath

Nature Communications, 2022, vol. 13, issue 1, 1-8

Abstract: Abstract Lithium-rich disordered rocksalt cathodes display high capacities arising from redox chemistry on both transition-metal ions (TM-redox) and oxygen ions (O-redox), making them promising candidates for next-generation lithium-ion batteries. However, the atomic-scale mechanisms governing O-redox behaviour in disordered structures are not fully understood. Here we show that, at high states of charge in the disordered rocksalt Li2MnO2F, transition metal migration is necessary for the formation of molecular O2 trapped in the bulk. Density functional theory calculations reveal that O2 is thermodynamically favoured over other oxidised O species, which is confirmed by resonant inelastic X-ray scattering data showing only O2 forms. When O-redox involves irreversible Mn migration, this mechanism results in a path-dependent voltage hysteresis between charge and discharge, commensurate with the hysteresis observed electrochemically. The implications are that irreversible transition metal migration should be suppressed to reduce the voltage hysteresis that afflicts O-redox disordered rocksalt cathodes.

Date: 2022
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-022-32983-w 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:13:y:2022:i:1:d:10.1038_s41467-022-32983-w

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

DOI: 10.1038/s41467-022-32983-w

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 (sonal.shukla@springer.com) and Springer Nature Abstracting and Indexing (indexing@springernature.com).

 
Page updated 2024-12-28
Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-32983-w