Stabilizing the Anionic Redox in 4.6 V LiCoO2 Cathode through Adjusting Oxygen Magnetic Moment

Weijin Kong; Deniz Wong; Ke An; Jicheng Zhang; Zhenhua Chen; Christian Schulz; Zijian Xu; Xiangfeng Liu

doi:10.1002/adfm.202202679

Stabilizing the Anionic Redox in 4.6 V LiCoO₂ Cathode through Adjusting Oxygen Magnetic Moment

Weijin Kong, Deniz Wong, Ke An, Jicheng Zhang, Zhenhua Chen, Christian Schulz, Zijian Xu, Xiangfeng Liu

Materials Engineering

Research output: Contribution to journal › Article › peer-review

29 Scopus citations

Abstract

The irreversible oxygen redox and the resulting structure degradation of LiCoO₂ at a high voltage cause very poor cycling performance. Herein, the anionic redox chemistry in 4.6 V LiCoO₂ cathode material through manipulating the oxygen magnetic moment (OMM) with oxygen vacancy and V doping is proposed to stabilize, and the relationship between OMM and the oxidation degree of oxygen is revealed. Oxygen vacancy induces the generation of OMM, and the synergy of oxygen vacancy and V doping reduces the change of OMM during charge/discharge processes. This mitigates the oxidation degree of oxygen and improves the reversibility of oxygen redox, which greatly inhibits the irreversible oxygen escape. The oxygen vacancies can further reduce the overlap of the electron clouds and lower the O 2p band center thus decreasing the oxygen redox activity. Moreover, the introduced V also increases the energy barrier of the phase transition and suppresses the irreversible phase transition and Co migration. The irreversible O₂ release is significantly inhibited and the cycling stability at 4.6 V is largely enhanced. This study presents the relationship between OMM and the oxidation degree of oxygen and provides some insights into improving the anion redox reversibility through adjusting the oxygen magnetic moment.

Original language	English
Article number	2202679
Journal	Advanced Functional Materials
Volume	32
Issue number	31
DOIs	https://doi.org/10.1002/adfm.202202679
State	Published - Aug 1 2022

Funding

This work was supported by National Natural Science Foundation of China (grant nos. 11975238, 22005302, and 11575192), the Scientific Instrument Developing Project (grant no. ZDKYYQ20170001), the International Partnership Program (grant nos. 211211KYSB20170060 and 211211KYSB20180020) of the Chinese Academy of Sciences, and Natural Science Foundation of Beijing Municipality (grant no. 2182082). This work was also supported by the Fundamental Research Funds for the Central Universities and the China Postdoctoral Science Foundation (2020M680648). The research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This work was supported by National Natural Science Foundation of China (grant nos. 11975238, 22005302, and 11575192), the Scientific Instrument Developing Project (grant no. ZDKYYQ20170001), the International Partnership Program (grant nos. 211211KYSB20170060 and 211211KYSB20180020) of the Chinese Academy of Sciences, and Natural Science Foundation of Beijing Municipality (grant no. 2182082). This work was also supported by the Fundamental Research Funds for the Central Universities and the China Postdoctoral Science Foundation (2020M680648). The research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

Funders	Funder number
Scientific Instrument Developing Project	211211KYSB20180020, ZDKYYQ20170001, 211211KYSB20170060
Office of Science
Oak Ridge National Laboratory
National Natural Science Foundation of China	22005302, 11575192, 11975238
Chinese Academy of Sciences
China Postdoctoral Science Foundation	2020M680648
Natural Science Foundation of Beijing Municipality	2182082
Fundamental Research Funds for the Central Universities

Keywords

4.6 V LiCoO
V doping
oxygen magnetic moment
oxygen release
oxygen vacancies

Access to Document

10.1002/adfm.202202679

Cite this

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abstract = "The irreversible oxygen redox and the resulting structure degradation of LiCoO2 at a high voltage cause very poor cycling performance. Herein, the anionic redox chemistry in 4.6 V LiCoO2 cathode material through manipulating the oxygen magnetic moment (OMM) with oxygen vacancy and V doping is proposed to stabilize, and the relationship between OMM and the oxidation degree of oxygen is revealed. Oxygen vacancy induces the generation of OMM, and the synergy of oxygen vacancy and V doping reduces the change of OMM during charge/discharge processes. This mitigates the oxidation degree of oxygen and improves the reversibility of oxygen redox, which greatly inhibits the irreversible oxygen escape. The oxygen vacancies can further reduce the overlap of the electron clouds and lower the O 2p band center thus decreasing the oxygen redox activity. Moreover, the introduced V also increases the energy barrier of the phase transition and suppresses the irreversible phase transition and Co migration. The irreversible O2 release is significantly inhibited and the cycling stability at 4.6 V is largely enhanced. This study presents the relationship between OMM and the oxidation degree of oxygen and provides some insights into improving the anion redox reversibility through adjusting the oxygen magnetic moment.",

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AU - Xu, Zijian

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N2 - The irreversible oxygen redox and the resulting structure degradation of LiCoO2 at a high voltage cause very poor cycling performance. Herein, the anionic redox chemistry in 4.6 V LiCoO2 cathode material through manipulating the oxygen magnetic moment (OMM) with oxygen vacancy and V doping is proposed to stabilize, and the relationship between OMM and the oxidation degree of oxygen is revealed. Oxygen vacancy induces the generation of OMM, and the synergy of oxygen vacancy and V doping reduces the change of OMM during charge/discharge processes. This mitigates the oxidation degree of oxygen and improves the reversibility of oxygen redox, which greatly inhibits the irreversible oxygen escape. The oxygen vacancies can further reduce the overlap of the electron clouds and lower the O 2p band center thus decreasing the oxygen redox activity. Moreover, the introduced V also increases the energy barrier of the phase transition and suppresses the irreversible phase transition and Co migration. The irreversible O2 release is significantly inhibited and the cycling stability at 4.6 V is largely enhanced. This study presents the relationship between OMM and the oxidation degree of oxygen and provides some insights into improving the anion redox reversibility through adjusting the oxygen magnetic moment.

AB - The irreversible oxygen redox and the resulting structure degradation of LiCoO2 at a high voltage cause very poor cycling performance. Herein, the anionic redox chemistry in 4.6 V LiCoO2 cathode material through manipulating the oxygen magnetic moment (OMM) with oxygen vacancy and V doping is proposed to stabilize, and the relationship between OMM and the oxidation degree of oxygen is revealed. Oxygen vacancy induces the generation of OMM, and the synergy of oxygen vacancy and V doping reduces the change of OMM during charge/discharge processes. This mitigates the oxidation degree of oxygen and improves the reversibility of oxygen redox, which greatly inhibits the irreversible oxygen escape. The oxygen vacancies can further reduce the overlap of the electron clouds and lower the O 2p band center thus decreasing the oxygen redox activity. Moreover, the introduced V also increases the energy barrier of the phase transition and suppresses the irreversible phase transition and Co migration. The irreversible O2 release is significantly inhibited and the cycling stability at 4.6 V is largely enhanced. This study presents the relationship between OMM and the oxidation degree of oxygen and provides some insights into improving the anion redox reversibility through adjusting the oxygen magnetic moment.

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