Two-Electron Reaction without Structural Phase Transition in Nanoporous Cathode Material

We investigated the charge/discharge properties, valence states, and structural properties of a nanoporous cathode materialLixMn[Fe(CN)6]0.83·3.5H2O. The film-type electrode ofLixMn[Fe(CN)6]0.83·3.5H2Oexhibited a high charge capacity(=128 mAh g-1)and a good cyclability (87% of the initial value after 100 cycles) and is one of the promising candidates for Li-ion battery cathode. X-ray absorption spectra near the Fe and Mn K-edges revealed that the charge/discharge process is a two-electron reaction; that is,MnII–NC–FeII,MnII–NC–FeIII, andMnIII–NC–FeIII. We further found that the crystal structure remains cubic throughout the charge/discharge process. The lattice constant slightly increased during the[FeII(CN)6]4-/[FeIII(CN)6]3-oxidization reaction while decreased during theMnII/MnIIIoxidization reaction. The two-electron reaction without structural phase transition is responsible for the high charge capacity and the good cyclability.