Detailing the self-discharge of a cathode based on a prussian blue analogue

Prussian Blue analogues (PBAs) are a promising class of electrode active materials for batteries. Among them, copper nitroprusside, Cu[Fe(CN)5NO], has recently been investigated for its peculiar redox system, which also involves the nitrosyl ligand as a non-innocent ligand, in addition to the electroactivity of the metal sites, Cu and Fe. This paper studies the dynamics of the electrode, employing surface sensitive X-ray Photoelectron spectroscopy (XPS) and bulk sensitive X-ray absorption spectroscopy (XAS) techniques. XPS provided chemical information on the layers formed on electrode surfaces following the self-discharge process of the cathode material in the presence of the electrolyte. These layers consist mainly of electrolyte degradation products, such as LiF, LixPOyFz and LixPFy. Moreover, as evidenced by XAS and XPS, reduction at both metal sites takes place in the bulk and in the surface of the material, clearly evidencing that a self-discharge process is occurring. We observed faster processes and higher amounts of reduced species and decomposition products in the case of samples with a higher amount of coordination water.