Unveiling the Energy Storage Mechanism of MnO2 Polymorphs for Zinc-Manganese Dioxide Batteries

Qingyong Zhang; Jun Zhao; Xiuyuan Chen; Ruijie Yang; Ting Ying; Chong Cheng; Bilu Liu; Jun Fan; Shuang Li; Zhiyuan Zeng

doi:10.1002/adfm.202306652

Unveiling the Energy Storage Mechanism of MnO₂ Polymorphs for Zinc-Manganese Dioxide Batteries

Qingyong Zhang, Jun Zhao, Xiuyuan Chen, Ruijie Yang, Ting Ying, Chong Cheng, Bilu Liu, Jun Fan^*, Shuang Li^*, Zhiyuan Zeng^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

56 Citations (Scopus)

Abstract

The energy storage mechanism of MnO₂ in aqueous zinc ion batteries (ZIBs) is investigated using four types of MnO₂ with crystal phases corresponding to α-, β-, γ-, and δ-MnO₂. Experimental and theoretical calculation results reveal that all MnO₂ follow the H⁺ and Zn²⁺ co-intercalation mechanism during discharge, with ZnMn₂O₄, MnOOH, and Zn₄(SO₄)(OH)₆·4H₂O being the main products. ZnMn₂O₄ is formed from Zn²⁺ intercalation, while MnOOH and Zn₄(SO₄)(OH)₆·4H₂O are formed from H⁺ intercalation. Charging generates MnO₂ through the extraction of Zn²⁺ and H⁺ from ZnMn₂O₄ and MnOOH, indicating reversible reactions. The study also reveals that H⁺ intercalation exhibits better kinetics than Zn²⁺ intercalation due to its higher diffusion ability and easier charge transfer. The crystal structures and diffusion energy barriers differences are responsible for the differences of H⁺ and Zn²⁺ diffusion in MnO₂, with the layered δ phase exhibiting the lowest diffusion energy barrier and highest apparent diffusion coefficient, while the α phase exhibits the highest diffusion energy barrier and lowest apparent diffusion coefficient. These findings highlight the importance of crystal phases in determining the diffusion ability and energy storage of MnO₂, which can inform strategies for design of multiphase MnO₂ cathodes for high-performance ZIBs. © 2024 Wiley-VCH GmbH.

Original language	English
Article number	2306652
Journal	Advanced Functional Materials
Volume	34
Issue number	30
Online published	27 Mar 2024
DOIs	https://doi.org/10.1002/adfm.202306652
Publication status	Published - 24 Jul 2024

Funding

Q.Z. and J.Z. contributed equally to this work. Z.Y.Z. thanks the General Research Fund support from the Research Grants Council of the Hong Kong Special Administrative Region, China [Project No. CityU11308923] and the Basic Research Project from Shenzhen Science and Technology Innovation Committee in Shenzhen, China [no. JCYJ20210324134012034], and the Applied Research Grant of City University of Hong Kong (project no of 9667247) and Chow Sang Sang Group Research Fund of City University of Hong Kong (project no of 9229123). Z.Y. Z. also thanks the funding supported by the Seed Collaborative Research Fund Scheme of State Key Laboratory of Marine Pollution which receives regular research funding from Innovation and Technology Commission (ITC) of the Hong Kong SAR Government. However, any opinions, findings, conclusions or recommendations expressed in this publication do not reflect the views of the Hong Kong SAR Government or the ITC.

Research Keywords

co-intercalation
diffusion ability
MnO2 polymorphs
Zinc ion batteries

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RGC-funded

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10.1002/adfm.202306652

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title = "Unveiling the Energy Storage Mechanism of MnO2 Polymorphs for Zinc-Manganese Dioxide Batteries",

abstract = "The energy storage mechanism of MnO2 in aqueous zinc ion batteries (ZIBs) is investigated using four types of MnO2 with crystal phases corresponding to α-, β-, γ-, and δ-MnO2. Experimental and theoretical calculation results reveal that all MnO2 follow the H+ and Zn2+ co-intercalation mechanism during discharge, with ZnMn2O4, MnOOH, and Zn4(SO4)(OH)6·4H2O being the main products. ZnMn2O4 is formed from Zn2+ intercalation, while MnOOH and Zn4(SO4)(OH)6·4H2O are formed from H+ intercalation. Charging generates MnO2 through the extraction of Zn2+ and H+ from ZnMn2O4 and MnOOH, indicating reversible reactions. The study also reveals that H+ intercalation exhibits better kinetics than Zn2+ intercalation due to its higher diffusion ability and easier charge transfer. The crystal structures and diffusion energy barriers differences are responsible for the differences of H+ and Zn2+ diffusion in MnO2, with the layered δ phase exhibiting the lowest diffusion energy barrier and highest apparent diffusion coefficient, while the α phase exhibits the highest diffusion energy barrier and lowest apparent diffusion coefficient. These findings highlight the importance of crystal phases in determining the diffusion ability and energy storage of MnO2, which can inform strategies for design of multiphase MnO2 cathodes for high-performance ZIBs. {\textcopyright} 2024 Wiley-VCH GmbH.",

keywords = "co-intercalation, diffusion ability, MnO2 polymorphs, Zinc ion batteries",

author = "Qingyong Zhang and Jun Zhao and Xiuyuan Chen and Ruijie Yang and Ting Ying and Chong Cheng and Bilu Liu and Jun Fan and Shuang Li and Zhiyuan Zeng",

year = "2024",

month = jul,

day = "24",

doi = "10.1002/adfm.202306652",

language = "English",

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TY - JOUR

T1 - Unveiling the Energy Storage Mechanism of MnO2 Polymorphs for Zinc-Manganese Dioxide Batteries

AU - Zhang, Qingyong

AU - Zhao, Jun

AU - Chen, Xiuyuan

AU - Yang, Ruijie

AU - Ying, Ting

AU - Cheng, Chong

AU - Liu, Bilu

AU - Fan, Jun

AU - Li, Shuang

AU - Zeng, Zhiyuan

PY - 2024/7/24

Y1 - 2024/7/24

N2 - The energy storage mechanism of MnO2 in aqueous zinc ion batteries (ZIBs) is investigated using four types of MnO2 with crystal phases corresponding to α-, β-, γ-, and δ-MnO2. Experimental and theoretical calculation results reveal that all MnO2 follow the H+ and Zn2+ co-intercalation mechanism during discharge, with ZnMn2O4, MnOOH, and Zn4(SO4)(OH)6·4H2O being the main products. ZnMn2O4 is formed from Zn2+ intercalation, while MnOOH and Zn4(SO4)(OH)6·4H2O are formed from H+ intercalation. Charging generates MnO2 through the extraction of Zn2+ and H+ from ZnMn2O4 and MnOOH, indicating reversible reactions. The study also reveals that H+ intercalation exhibits better kinetics than Zn2+ intercalation due to its higher diffusion ability and easier charge transfer. The crystal structures and diffusion energy barriers differences are responsible for the differences of H+ and Zn2+ diffusion in MnO2, with the layered δ phase exhibiting the lowest diffusion energy barrier and highest apparent diffusion coefficient, while the α phase exhibits the highest diffusion energy barrier and lowest apparent diffusion coefficient. These findings highlight the importance of crystal phases in determining the diffusion ability and energy storage of MnO2, which can inform strategies for design of multiphase MnO2 cathodes for high-performance ZIBs. © 2024 Wiley-VCH GmbH.

AB - The energy storage mechanism of MnO2 in aqueous zinc ion batteries (ZIBs) is investigated using four types of MnO2 with crystal phases corresponding to α-, β-, γ-, and δ-MnO2. Experimental and theoretical calculation results reveal that all MnO2 follow the H+ and Zn2+ co-intercalation mechanism during discharge, with ZnMn2O4, MnOOH, and Zn4(SO4)(OH)6·4H2O being the main products. ZnMn2O4 is formed from Zn2+ intercalation, while MnOOH and Zn4(SO4)(OH)6·4H2O are formed from H+ intercalation. Charging generates MnO2 through the extraction of Zn2+ and H+ from ZnMn2O4 and MnOOH, indicating reversible reactions. The study also reveals that H+ intercalation exhibits better kinetics than Zn2+ intercalation due to its higher diffusion ability and easier charge transfer. The crystal structures and diffusion energy barriers differences are responsible for the differences of H+ and Zn2+ diffusion in MnO2, with the layered δ phase exhibiting the lowest diffusion energy barrier and highest apparent diffusion coefficient, while the α phase exhibits the highest diffusion energy barrier and lowest apparent diffusion coefficient. These findings highlight the importance of crystal phases in determining the diffusion ability and energy storage of MnO2, which can inform strategies for design of multiphase MnO2 cathodes for high-performance ZIBs. © 2024 Wiley-VCH GmbH.

KW - co-intercalation

KW - diffusion ability

KW - MnO2 polymorphs

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DO - 10.1002/adfm.202306652

M3 - RGC 21 - Publication in refereed journal

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JO - Advanced Functional Materials

JF - Advanced Functional Materials

IS - 30

M1 - 2306652

ER -

Unveiling the Energy Storage Mechanism of MnO₂ Polymorphs for Zinc-Manganese Dioxide Batteries

Abstract

Funding

Research Keywords

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GRF: An Electrochemical Lithium Intercalation and Exfoliation Strategy on 2D Transition Metal Dichalcogenides for Phase Tuning and Energy Application

DON_RMG: Development of MnO2-based Catalysts for Efficient Removal of Volatile Organic Compounds - RMGS

Cite this

Unveiling the Energy Storage Mechanism of MnO2 Polymorphs for Zinc-Manganese Dioxide Batteries

Abstract

Funding

Research Keywords

RGC Funding Information

Access Output

Other Access Options

Permanent Link

Other Files and Links

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Projects

GRF: An Electrochemical Lithium Intercalation and Exfoliation Strategy on 2D Transition Metal Dichalcogenides for Phase Tuning and Energy Application

DON_RMG: Development of MnO2-based Catalysts for Efficient Removal of Volatile Organic Compounds - RMGS

Cite this

Unveiling the Energy Storage Mechanism of MnO₂ Polymorphs for Zinc-Manganese Dioxide Batteries