Issue 44, 2023

Reversible Cl/Cl redox in a spinel Mn3O4 electrode

Abstract

A unique prospect of using halides as charge carriers is the possibility of the halides undergoing anodic redox behaviors when serving as charge carriers for the charge-neutrality compensation of electrodes. However, the anodic conversion of halides to neutral halogen species has often been irreversible at room temperature due to the emergence of diatomic halogen gaseous products. Here, we report that chloride ions can be reversibly converted to near-neutral atomic chlorine species in the Mn3O4 electrode at room temperature in a highly concentrated chloride-based aqueous electrolyte. Notably, the Zn2+ cations inserted in the first discharge and trapped in the Mn3O4 structure create an environment to stabilize the converted chlorine atoms within the structure. Characterization results suggest that the Cl/Cl redox is responsible for the observed large capacity, as the oxidation state of Mn barely changes upon charging. Computation results corroborate that the converted chlorine species exist as polychloride monoanions, e.g., [Cl3] and [Cl5], inside the Zn2+-trapped Mn3O4, and the presence of polychloride species is confirmed experimentally. Our results point to the halogen plating inside electrode lattices as a new charge-storage mechanism.

Graphical abstract: Reversible Cl/Cl− redox in a spinel Mn3O4 electrode

Supplementary files

Article information

Article type
Edge Article
Submitted
30 Aug 2023
Accepted
09 Oct 2023
First published
24 Oct 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 12645-12652

Reversible Cl/Cl redox in a spinel Mn3O4 electrode

S. K. Sandstrom, Q. Li, Y. Sui, M. Lyons, C. Chang, R. Zhang, H. Jiang, M. Yu, D. Hoang, W. F. Stickle, H. L. Xin, Z. Feng, D. Jiang and X. Ji, Chem. Sci., 2023, 14, 12645 DOI: 10.1039/D3SC04545E

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements