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

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.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002B-312F-4 Version Permalink: http://hdl.handle.net/21.11116/0000-0001-095D-E
Genre: Journal Article

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 Creators:
Mikhailova, Daria1, Author              
Karakulina, Olesia M.2, Author
Batuk, Dmitry2, Author
Hadermann, Joke2, Author
Abakumov, Artem M.2, Author
Herklotz, Markus2, Author
Tsirlin, Alexander A.2, Author
Oswald, Steffen2, Author
Giebeler, Lars2, Author
Schmidt, Marcus3, Author              
Eckert, Juergen2, Author
Knapp, Michael2, Author
Ehrenberg, Helmut2, Author
Affiliations:
1Daria Mikhailova, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863448              
2External Organizations, ou_persistent22              
3Marcus Schmidt, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863415              

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 Abstract: 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.

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Language(s): eng - English
 Dates: 2016-07-012016-07-01
 Publication Status: Published in print
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 55 (14) Sequence Number: - Start / End Page: 7079 - 7089 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669