Effect of Water and Alkali‐Ion Content on the Structure of Manganese(II) Hexacyanoferrate(II) by a Joint Operando X‐ray Absorption Spectroscopy and Chemometric Approach

Abstract Manganese hexacyanoferrate (MnHCF) is made of earth‐abundant elements by a safe and easy synthesis. The material features a higher specific capacity at a higher potential than other Prussian blue analogs. However, the effect of hydration is critical to determine the electrochemical performance as both the electrochemical behavior and the reaction dynamics are affected by interstitial/structural water and adsorbed water. In this study, the electrochemical activity of MnHCF is investigated by varying the interstitial ion content through a joint operando X‐ray absorption spectroscopy and chemometric approach, with the intent to assess the structural and electronic modifications that occur during Na release and Li insertion, as well as the overall dynamic evolution of the system. In MnHCF, both the Fe and Mn centers are electrochemically active and undergo reversible oxidation during the interstitial ion extraction (Fe 2+ /Fe 3+ and Mn 2+ /Mn 3+ ). The adsorption of water results in irreversible capacity during charge but only on the Fe site, which is suggested by our chemometric analysis. The local environment of Mn experiences a substantial yet reversible Jahn–Teller effect upon interstitial ion removal because of the formation of trivalent Mn, which is associated with a decrease of the equatorial Mn−N bond lengths by 10 %.