Inhibiting irreversible Zn²⁺/H⁺ co-insertion chemistry in aqueous zinc-MoOₓ batteries for enhanced capacity stability

Date

2025

Authors

Zheng, C.
Guan, X.
Huang, Z.
Mao, S.
Han, X.
Duan, X.
Li, H.
Ma, T.

Editors

Advisors

Journal Title

Journal ISSN

Volume Title

Type:

Journal article

Citation

Journal of Energy Chemistry, 2025; 102:98-106

Statement of Responsibility

Chen Zheng, Xinwei Guan, Zihang Huang, Shuai Mao, Xu Han, Xiaoguang Duan, Hui Li, Tianyi Ma

Conference Name

DOI

10.1016/j.jechem.2024.10.034

Abstract

Rechargeable aqueous Zn-MoOₓ batteries are promising energy storage devices with high theoretical specific capacity and low cost. However, MoO₃ cathodes suffer drastic capacity decay during the initial discharging/charging process in conventional electrolytes, resulting in a short cycle life and challenging the development of Zn-MoOₓ batteries. Here we comprehensively investigate the dissolution mechanism of MoO₃ cathodes and innovatively introduce a polymer to inhibit the irreversible processes. Our findings reveal that this capacity decay originates from the irreversible Zn²⁺/H⁺ co-intercalation/extraction process in aqueous electrolytes. Even worse, during Zn²⁺ intercalation, the formed ZnₓMoO₃−x intermediate phase with lower valence states (Mo⁵⁺/Mo⁴⁺) experiences severe dissolution in aqueous environments. To address these challenges, we developed a first instance of coating a polyaniline (PANI) shell around the MoO₃ nanorod effectively inhibiting these irreversible processes and protecting structural integrity during long-term cycling. Detailed structural analysis and theoretical calculations indicate that =N– groups in PANI@MoO₃−x simultaneously weaken H+ adsorption and enhance Zn²⁺ adsorption, which endowed the PANI@MoO₃−x– cathode with reversible Zn²⁺/H⁺ intercalation/extraction. Consequently, the obtained PANI@MoO₃−x cathode delivers an excellent discharge capacity of 316.86 mA hg¯¹ at 0.1 A g¯¹ and prolonged cycling stability of 75.49% capacity retention after 1000 cycles at 5 A g¯¹. This work addresses the critical issues associated with MoO₃ cathodes and significantly advances the understanding of competitive multi-ion energy storage mechanisms in aqueous Zn-MoO₃ batteries.

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Dissertation Note

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Description

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Rights

© 2024 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

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Grant ID

http://purl.org/au-research/grants/arc/FT210100298
 http://purl.org/au-research/grants/arc/DP220100603
 http://purl.org/au-research/grants/arc/LP210200504
 http://purl.org/au-research/grants/arc/LP220100088
 http://purl.org/au-research/grants/arc/LP230200897
 http://purl.org/au-research/grants/arc/IH240100009

Published Version

http://dx.doi.org/10.1016/j.jechem.2024.10.034

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Persistent link to this record

https://hdl.handle.net/2440/144986