Issue 2, 2024

Manganese dissolution in alkaline medium with and without concurrent oxygen evolution in LiMn2O4

Abstract

Manganese dissolution during the oxygen evolution reaction (OER) has been a persistent challenge that impedes the practical implementation of Mn-based electrocatalysts including the LixMn2O4 system in aqueous alkaline electrolyte. The investigated LiMn2O4 particles exhibit two distinct Mn dissolution processes; one independent of OER and the other associated with OER. Combining bulk sensitive X-ray absorption spectroscopy, surface sensitive X-ray photoelectron spectroscopy as well as detection of Mn dissolution by ICP-OES and by using a rotating ring-disk electrode, we explore the less understood Mn dissolution mechanism during OER. We correlate near-surface oxidation with the charge attributed to dissolved Mn, which indicates increasing Mn dissolution with the formation of surface Mn4+ species under an anodic potential. The stronger dissolution during the OER is attributed to the formation of additional Mn4+ from Mn3+ during OER. We discuss that control over the amount of Mn4+ in LixMn2O4 before the onset of the OER can partially mitigate the OER-triggered dissolution. Overall, our atomistic insights into the Mn dissolution processes are crucial for knowledge-guided mitigation of electrocatalyst degradation, which can be broadly extended to manganese-based oxide systems.

Graphical abstract: Manganese dissolution in alkaline medium with and without concurrent oxygen evolution in LiMn2O4

Supplementary files

Article information

Article type
Paper
Submitted
31 Aug 2023
Accepted
06 Jan 2024
First published
08 Jan 2024
This article is Open Access
Creative Commons BY license

Energy Adv., 2024,3, 504-514

Manganese dissolution in alkaline medium with and without concurrent oxygen evolution in LiMn2O4

O. Y. Bisen, M. Baumung, M. Tatzel, C. A. Volkert and M. Risch, Energy Adv., 2024, 3, 504 DOI: 10.1039/D3YA00434A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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