Effect of the Interaction between Transition Metal Redox Center and Cyanide Ligand on Structural Evolution in Prussian White Cathodes

Transition metal (TM) based Prussian whites, comprising a cyanide anion ((C equivalent to N)(-)) and TM cations in an alternative manner, have been widely adopted as cathode materials for rechargeable batteries. Prussian whites are characterized by the TM electronic states that exclusively adopt low spin (LS) toward the C atom and high spin (HS) toward the N atom through the hybridized covalent bonding in the TM & horbar;C equivalent to N & horbar;TM unit with the average oxidation states of the TM ions being 2+, considerably affecting the phase transition behavior upon the release and storage of carrier ions; however, there have been only a few studies on their associated features. Herein, Prussian whites with different HS TM ions were synthesized via coprecipitation and the phase transition behavior controlled by the pi electron interaction between the cyanide anions and TM ions during battery operations was investigated. In situ X-ray characterizations reveal that the combined effect of pi backdonation in the LS Fe-C unit and pi donation in the HS TM-N unit effectively controls the bond length of the TM & horbar;C equivalent to N & horbar;TM building unit, thus markedly influencing the lattice volume of a series of Prussian white cathodes during the charge/discharge process. This study presents a comprehensive understanding of the structure-property relationship of the Prussian white cathodes involving pi electron interactions during battery operations.