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

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 to OER. Combining the bulk sensitive X-ray absorption spectroscopy, surface sensitive X-ray photoelectron spectroscopy and electrochemical detection of Mn dissolution using 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 demonstrates increasing Mn dissolution with the formation of surface Mn4+ species under anodic potential. The observed stronger dissolution during the OER is attributed to the formation of additional Mn4+ from Mn3+ during OER. We show 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.