Lithium intercalation properties in manganese-iron Prussian blue analogues

Abstract

We investigated the electronic states and structural properties of LixMn[Fe(CN)6]0.83·3.5H2O, and LixMn[Fe(CN)6]0.87·2.6H2O, which have different amount of [Fe(CN)6] vacancies. X-ray absorption spectra near the Fe and Mn K-edges revealed that the Li intercalation/deintercalation process is two-electron reaction, i.e. MnII - NC - FeII, Mn II - NC - FeIII, and MnIII - NC - Fe III. The crystal structure of LixMn[Fe(CN)6]0.83·3.5H2O remains cubic and single phase throughout the Li intercalation/deintercalation process. The crystal structure of LixMn[Fe(CN)6]0.87·2.6H2O is also cubic, while phase separation of Li+-rich phase and Li +-poor phase was observed during the MnII/MnIII reduction/oxidation process.