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Nano Research 2023, 16(2): 2511-2518 https://doi.org/10.1007/s12274-022-5057-0
Research Article | Issue | Published: 30 November 2022

Mo doping provokes two electron reaction in MnO2 with ultrahigh capacity for aqueous zinc ion batteries

Show Author's Information Xiaoyu Xia§,  Yajun Zhao§,  Yi Zhao§,  Minggui Xu,  Wen Liu( ),  Xiaoming Sun( )
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China

§ Xiaoyu Xia, Yajun Zhao, and Yi Zhao contributed equally to this work.

Keywords:
high energy density, zinc ion batteries, Mo-doped MnO2, Jahn–Teller distortion, two-electron reaction
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Xia X, Zhao Y, Zhao Y, et al. Mo doping provokes two electron reaction in MnO2 with ultrahigh capacity for aqueous zinc ion batteries. Nano Research, 2023, 16(2): 2511-2518. https://doi.org/10.1007/s12274-022-5057-0
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Abstract Full text Electronic supplementary material About this article

Rechargeable aqueous zinc ion batteries (AZIBs) based on manganese dioxide (MnO2) have received much attention for large-scale energy storage applications, however, their energy density is mainly limited by the one-electron reaction of Mn4+/Mn3+ redox. Herein, Mo doped δ-MnO2 (Mo-MnO2) is prepared and used as a high-performance cathode for AZIBs, which delivers an ultrahigh specific capacity of 652 mAh·g−1 at 0.2 A·g−1 based on the two-step two-electron redox reaction of Mn4+ ⇌ Mn3+ ⇌ Mn2+. Ex-situ structural analysis and density functional theory calculation reveal that the Mo5+ dopant plays an important role in enhancing the electronic conductivity of Mo-MnO2 and promoting Jahn–Teller distortion of octahedral [MnO6] in ZnMn2O4, which facilitates the second step redox reaction of Mn3+/Mn2+. This work provides a novel cathode materials design with multi-electron redox chemistry to achieve high energy density in AZIBs.


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Electronic supplementary material
About this article

Mo doping provokes two electron reaction in MnO2 with ultrahigh capacity for aqueous zinc ion batteries

Show Author's information Xiaoyu Xia§, Yajun Zhao§, Yi Zhao§, Minggui Xu, Wen Liu( ), Xiaoming Sun( )
State Key Laboratory of Chemical Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China

§ Xiaoyu Xia, Yajun Zhao, and Yi Zhao contributed equally to this work.

Abstract

Rechargeable aqueous zinc ion batteries (AZIBs) based on manganese dioxide (MnO2) have received much attention for large-scale energy storage applications, however, their energy density is mainly limited by the one-electron reaction of Mn4+/Mn3+ redox. Herein, Mo doped δ-MnO2 (Mo-MnO2) is prepared and used as a high-performance cathode for AZIBs, which delivers an ultrahigh specific capacity of 652 mAh·g−1 at 0.2 A·g−1 based on the two-step two-electron redox reaction of Mn4+ ⇌ Mn3+ ⇌ Mn2+. Ex-situ structural analysis and density functional theory calculation reveal that the Mo5+ dopant plays an important role in enhancing the electronic conductivity of Mo-MnO2 and promoting Jahn–Teller distortion of octahedral [MnO6] in ZnMn2O4, which facilitates the second step redox reaction of Mn3+/Mn2+. This work provides a novel cathode materials design with multi-electron redox chemistry to achieve high energy density in AZIBs.

Keywords: high energy density, zinc ion batteries, Mo-doped MnO2, Jahn–Teller distortion, two-electron reaction

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Publication history
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Acknowledgements

Publication history

Received: 01 August 2022
Revised: 12 September 2022
Accepted: 14 September 2022
Published: 30 November 2022
Issue date: February 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21935001 and 22101015), the National Key Research and Development Program of China (No. 2018YFA0702002), and the Program for Changjiang Scholars and Innovation Research Team in the University (No. IRT1205).

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