Deutsch
 
Hilfe Datenschutzhinweis Impressum
  DetailsucheBrowse

Datensatz

DATENSATZ AKTIONENEXPORT

Freigegeben

Zeitschriftenartikel

Layered-to-Tunnel Structure Transformation and Oxygen Redox Chemistry in LiRhO2 upon Li Extraction and Insertion

MPG-Autoren
/persons/resource/persons126756

Mikhailova,  Daria
Daria Mikhailova, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

/persons/resource/persons126835

Schmidt,  Marcus
Marcus Schmidt, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

Externe Ressourcen
Es sind keine externen Ressourcen hinterlegt
Volltexte (beschränkter Zugriff)
Für Ihren IP-Bereich sind aktuell keine Volltexte freigegeben.
Volltexte (frei zugänglich)
Es sind keine frei zugänglichen Volltexte in PuRe verfügbar
Ergänzendes Material (frei zugänglich)
Es sind keine frei zugänglichen Ergänzenden Materialien verfügbar
Zitation

Mikhailova, D., Karakulina, O. M., Batuk, D., Hadermann, J., Abakumov, A. M., Herklotz, M., et al. (2016). Layered-to-Tunnel Structure Transformation and Oxygen Redox Chemistry in LiRhO2 upon Li Extraction and Insertion. Inorganic Chemistry, 55(14), 7079-7089. doi:10.1021/acs.inorgchem.6b01008.


Zitierlink: https://hdl.handle.net/11858/00-001M-0000-002B-312F-4
Zusammenfassung
Layered Li(M,Li)O-2 (where M is a transition metal) ordered rock-salt-type structures are used in advanced metal-ion batteries as one of the best hosts for the reversible intercalation of Li ions. Besides the conventional redox reaction involving oxidation/reduction of the M cation upon Li extraction/insertion, creating oxygen-located holes because of the partial oxygen oxidation increases capacity while maintaining the oxidized oxygen species in the lattice through high covalency of the M-O bonding. Typical degradation mechanism of the Li(M,Li)O-2 electrodes involves partially irreversible M cation migration toward the Li positions, resulting in gradual capacity/voltage fade. Here, using LiRhO2 as a model system (isostructural and isoelectronic to LiCoO2), for the first time, we demonstrate an intimate coupling between the oxygen redox and M cation migration. A formation of the oxidized oxygen species upon electrochemical Li extraction coincides with transformation of the layered Li1-xRhO2 structure into the gamma-MnO2-type rutile-ramsdellite intergrowth LiyRh3O6 structure with rutile-like [1 x 1] channels along with bigger ramsdellite-like [2 x 1] tunnels through massive and concerted Rh migration toward the empty positions in the Li layers. The oxidized oxygen dimers with the O-O distances as short as 2.26 angstrom are stabilized in this structure via the local Rh-O configuration reminiscent to that in the mu-peroxo-mu-hydroxo Rh complexes. The LiyRh3O6 structure is remarkably stable upon electrochemical cycling illustrating that proper structural implementation of the oxidized oxygen species can open a pathway toward deliberate employment of the anion redox chemistry in high-capacity/high-voltage positive electrodes for metal-ion batteries.