Local structure of hydrated and dehydrated Prussian white cathode materials

Abstract

The sodium iron hexacyanoferrate compound with chemical formula Na_2.04(2)Fe[Fe(CN)₆]·2.24(2)H₂O, also known as Prussian white (PW), contains disordered and dynamic water molecules that have a dualistic effect on its battery performance. Furthermore, the material exhibits severe strain when dehydrated, which over time diminishes the performance. To understand the complex role of water on the sodium ion conduction and the structural changes happening upon dehydration, local structural characterization is needed. Here, we report the first neutron total scattering study of PW. Reverse Monte Carlo (RMC) fitting reveals that local octahedral distortion of the nitrogen-bound iron octahedra contributes to the disorder of the framework. The strain observed in the dehydrated material comes from a combination of the Fe–N bond elongation and a disordered distribution of sodium throughout the larger structure. In the hydrated material, the sodium exhibits more order due to the presence of water, which constrains the sodium movement. However, the sodium ordering affects the orientation of the water molecules. In the low temperature P2₁/n phase, sodium orders into planes with the oxygen atoms in the water molecules being in the plane, while the hydrogen atoms are pointing away from the sodium plane. In the room temperature R phase, the sodium and water are less ordered despite similar frameworks. Sodium can take a wide range of positions, especially if no water molecule blocks its way, to obtain optimal bonding conditions. These results show that the relationship between sodium and water is co-dependent, and demonstrate that the local structure of framework materials has a crucial link to their properties.