Regulation of Oxygen Redox in Disordered Rock-Salt LiXO₂ Li-Ion Cathodes by Cation Effects: A First-Principles Study

Area of Science:

• Materials Science
• Electrochemistry
• Computational Chemistry

Background:

• Anionic redox reactions significantly improve oxide cathode material performance.
• Disordered rock-salt (DRX) structures offer unique flexibility for cathode design.

Purpose of the Study:

• To elucidate the mechanisms of anionic redox in DRX cathode materials.
• To establish a framework for understanding cation influence on anion redox.
• To guide the rational design of high-performance DRX cathodes.

Main Methods:

• First-principles calculations
• Qualitative evaluation of oxygen coordination environment
• Quantitative analysis of metal-oxygen electronic states
• Systematic magnetic characterization

Main Results:

• Identified two anion redox mechanisms: reversible reductive coupling and irreversible oxygen dimerization.
• Established a three-tier framework categorizing cation participation in oxygen redox.
• Demonstrated that cationic doping can effectively regulate oxygen redox behavior.

Conclusions:

• Cation choice critically influences anionic redox activity in DRX cathodes.
• Understanding these mechanisms enables targeted design of advanced battery materials.
• This work provides a foundation for developing durable and high-performance DRX cathode materials.