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Updated: Jan 15, 2026

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques
Published on: November 11, 2013
Lithium ions protected orbital symmetry enables reversible oxygen redox in layered manganese-based cathodes
Ang Gao1, Shiguang Zhang2, Xiaohui Rong2
1Institute of Environmental and Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan 430079, China; Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education, Central China Normal University, Wuhan 430079, China; Wuhan Institute of Photochemistry and Technology, Wuhan 430083, China.
Abstract:
With a high capacity at low cost, manganese oxides utilizing oxygen redox chemistry are desirable candidates for replacing nickel- and cobalt-based cathodes. However, they suffer from rapid oxygen activity fading, commonly related to bonding interactions between the transition metals and oxygen, while receiving limited attention on the role of Li ions. Here, we demonstrated the protective role of Li ions in maintaining oxygen orbital symmetry to improve oxygen redox reversibility. The orbital symmetry breaking induced by Li ion migration leads to a disproportionation of oxygen during charging. This results in some oxygen becoming overoxidized and labile, compromising the structure and cycling stability. This mechanism is validated through experiments on P3-Na0.6Li0.2Mn0.8O2 and other layered manganese-based cathodes, as well via dynamic simulations. Finally, employing P2-Na0.75Li0.25Mn0.75O2, we propose a design strategy for stabilizing Li ions via electrostatic field disordering, enhancing the capacity retention over 150 cycles from 46% to 72%. The insights open an avenue towards the rational design of high-performance manganese-based cathodes.
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