Destabilization of Oxidized Lattice Oxygen in Layered Oxide Cathode.
ACS Nano
; 18(20): 13397-13405, 2024 May 21.
Article
in En
| MEDLINE
| ID: mdl-38728672
ABSTRACT
Integrating anion-redox capacity with orthodox cation-redox capacity is deemed as a promising solution for high-energy-density battery cathodes surmounting the present technical bottlenecks. However, the evolution of oxidized oxygen species during the electrochemical or chemical process easily jeopardizes the reversibility of oxygen redox and remains poorly understood. Herein, we showcase the gradual conversion of the π-interacting oxygen (localized hole states on O) to the σ-interacting oxygen upon resting at a high voltage for P3-type Na0.6Li0.2Mn0.8O2 with nominally stable ribbon-like superstructure, accompanied by the O-O dimerization and the local structural reorganization. We further pinpoint an abnormal Li+ migration process from the alkali-metal layer to the transition-metal layer for desodiated P3-Na0.6Li0.2Mn0.8O2, thereby leading to a partial reconstruction of the ribbon superstructure. The high-voltage plateau of oxygen-redox cathodes is concluded to be exclusively controlled by the oxygen stabilization mechanism rather than the superstructure ordering. In addition, there exists a kinetic competition between π and σ interaction during the uninterrupted electrochemical process.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
ACS Nano
Year:
2024
Document type:
Article
Affiliation country:
China
Publication country:
EEUU
/
ESTADOS UNIDOS
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ESTADOS UNIDOS DA AMERICA
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EUA
/
UNITED STATES
/
UNITED STATES OF AMERICA
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US
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USA