Shielding Mn³⁺ Disproportionation with Graphitic Carbon-Interlayered Manganese Oxide Cathodes for Enhanced Aqueous Energy Storage System

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Date

2024

Authors

Zhang, Y.
Han, X.
Huang, Z.H.
Lei, L.
Duan, X.
Li, H.
Ma, T.

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Journal Title

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Journal article

Citation

Small, 2024; 20(6):2401849-1-2401849-10

Statement of Responsibility

Yue Zhang, Xu Han, Zi-Hang Huang, Lei Lei, Xiaoguang Duan, Hui Li, and Tianyi Ma

Conference Name

DOI

10.1002/smll.202401849

Abstract

Manganese dioxide (MnO2) materials have recently garnered attention as prospective high-capacity cathodes, owing to their theoretical two-electron redox reaction in charge storage processes. However, their practical application in aqueous energy storage systems faces a formidable challenge: the disproportionation of Mn3+ ions, leading to a significant reduction in their capacity. To address this limitation, the study presents a novel graphitic carbon interlayer-engineered manganese oxide (CI-MnOx) characterized by an open structure and abundant defects. This innovative material serves several essential functions for efficient aqueous energy storage. First, a graphitic carbon layer coats the MnOx molecular interlayer, effectively inhibiting Mn3+ disproportionation and substantially enhancing electrode conductivity. Second, the phase variation within MnOx generates numerous crystal defects, vacancies, and active sites, optimizing electron-transfer capability. Third, the flexible carbon layer acts as a buffer, mitigating the volume expansion of MnOx during extended cycling. The synergistic effects of these features result in the CI-MnOx exhibiting an impressive high capacity of 272 mAh g-1 (1224 F g-1) at 0.25 A g-1. Notably, the CI-MnOx demonstrates zero capacity loss after 90 000 cycles (≈3011 h), an uncommon longevity for manganese oxide materials. Spectral characterizations reveal reversible cation intercalation and conversion reactions with multielectron transfer in a LiCl electrolyte.

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Published online: April 29, 2024

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© 2024 The Authors. Small published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

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Grant ID

http://purl.org/au-research/grants/arc/FT210100298
 http://purl.org/au-research/grants/arc/FT210100806
 http://purl.org/au-research/grants/arc/DP220100603
 http://purl.org/au-research/grants/arc/LP210100467
 http://purl.org/au-research/grants/arc/LP210200504
 http://purl.org/au-research/grants/arc/LP210200345
 http://purl.org/au-research/grants/arc/LP220100088
 http://purl.org/au-research/grants/arc/IC180100005

Published Version

https://doi.org/10.1002/smll.202401849

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Persistent link to this record

https://hdl.handle.net/2440/142575