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Nano Research 2024, 17(1): 221-227 https://doi.org/10.1007/s12274-023-5526-0
Research Article | Issue | Published: 15 March 2023

Optimal geometrical configuration and oxidation state of cobalt cations in spinel oxides to promote the performance of Li-O2 battery

Show Author's Information Yu Zhang1,§,  Shuting Zhang2,§,  Mengwei Yuan2,  Yufeng Li2,  Rong Liu3( ),  Caiyun Nan2( ),  Chen Chen1( )
Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China
Beijing Key Laboratory of Energy Conversion and Storage Materials Institution, College of Chemistry, Beijing Normal University, Beijing 100875, China
X-ray diffraction Lab, Analytical and Testing Center, Beijing Normal University, Beijing 100875, China

§ Yu Zhang and Shuting Zhang contributed equally to this work.

Keywords:
lithium peroxide, geometrical configuration, oxidation state, lithium oxygen (Li-O2) batteries
Topics:
Air batteries
Cite this article:
Zhang Y, Zhang S, Yuan M, et al. Optimal geometrical configuration and oxidation state of cobalt cations in spinel oxides to promote the performance of Li-O2 battery. Nano Research, 2024, 17(1): 221-227. https://doi.org/10.1007/s12274-023-5526-0
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Abstract Full text Electronic supplementary material About this article

Co3O4 is considered as one of promising cathode catalysts for lithium oxygen (Li-O2) batteries, which contains both tetrahedral Co2+ sites (Co2+Td) and octahedral Co3+ sites (Co3+Oh). It is important to reveal the effect of optimal geometric configuration and oxidation state of cobalt ion in Co3O4 to improve the performance of Li-O2 batteries. Herein, through regulating the synthesis process, Co2+ and Co3+ sites in Co3O4 were replaced with Zn and Al atoms to form materials with a unique Co site. The Li-O2 batteries based on ZnCo2O4 showed longer cycle life than that of CoAl2O4, suggesting that in Co3O4, the Co3+Oh site is a relatively better geometric configuration than Co2+Td site for Li-O2 batteries. Theoretical calculations revealed that Co3+Oh sites provide higher catalysis activity, regulating the adsorption energy of the intermediate LiO2 and accelerating the kinetics of the reaction in batteries, which further leads to the change of the morphology of the discharge product and ultimately improves the electrochemical performance of the batteries.


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Electronic supplementary material
About this article

Optimal geometrical configuration and oxidation state of cobalt cations in spinel oxides to promote the performance of Li-O2 battery

Show Author's information Yu Zhang1,§, Shuting Zhang2,§, Mengwei Yuan2, Yufeng Li2, Rong Liu3( ), Caiyun Nan2( ), Chen Chen1( )
Engineering Research Center of Advanced Rare Earth Materials, Department of Chemistry, Tsinghua University, Beijing 100084, China
Beijing Key Laboratory of Energy Conversion and Storage Materials Institution, College of Chemistry, Beijing Normal University, Beijing 100875, China
X-ray diffraction Lab, Analytical and Testing Center, Beijing Normal University, Beijing 100875, China

§ Yu Zhang and Shuting Zhang contributed equally to this work.

Abstract

Co3O4 is considered as one of promising cathode catalysts for lithium oxygen (Li-O2) batteries, which contains both tetrahedral Co2+ sites (Co2+Td) and octahedral Co3+ sites (Co3+Oh). It is important to reveal the effect of optimal geometric configuration and oxidation state of cobalt ion in Co3O4 to improve the performance of Li-O2 batteries. Herein, through regulating the synthesis process, Co2+ and Co3+ sites in Co3O4 were replaced with Zn and Al atoms to form materials with a unique Co site. The Li-O2 batteries based on ZnCo2O4 showed longer cycle life than that of CoAl2O4, suggesting that in Co3O4, the Co3+Oh site is a relatively better geometric configuration than Co2+Td site for Li-O2 batteries. Theoretical calculations revealed that Co3+Oh sites provide higher catalysis activity, regulating the adsorption energy of the intermediate LiO2 and accelerating the kinetics of the reaction in batteries, which further leads to the change of the morphology of the discharge product and ultimately improves the electrochemical performance of the batteries.

Keywords: lithium peroxide, geometrical configuration, oxidation state, lithium oxygen (Li-O2) batteries

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Publication history
Copyright
Acknowledgements

Publication history

Received: 30 November 2022
Revised: 14 January 2023
Accepted: 22 January 2023
Published: 15 March 2023
Issue date: January 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by the National Key R&D Program of China (No. 2021YFF0500503) and the National Natural Science Foundation of China (Nos. 21925202 and U22B2071). We thank the 1W1B station for XAFS measurement in Beijing Synchrotron Radiation Facility (BSRF).

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