Detailing the Self-Discharge of a Cathode Based on a Prussian Blue Analogue

Elisa Musella, Angelo Mullaliu, Thomas Ruf, Paula Huth, Domenica Tonelli, Giuliana Aquilanti, Reinhard Denecke and Marco Giorgetti
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Elisa Musella: Department of Industrial Chemistry “Toso Montanari”, University of Bologna, Viale Risorgimento 4, 40136 Bologna, Italy
Angelo Mullaliu: Department of Industrial Chemistry “Toso Montanari”, University of Bologna, Viale Risorgimento 4, 40136 Bologna, Italy
Thomas Ruf: Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstraße 2, D-04103 Leipzig, Germany
Paula Huth: Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstraße 2, D-04103 Leipzig, Germany
Domenica Tonelli: Department of Industrial Chemistry “Toso Montanari”, University of Bologna, Viale Risorgimento 4, 40136 Bologna, Italy
Giuliana Aquilanti: Elettra Sincrotrone Trieste S.C.p.A., s.s. 14 km 163.5, 34149 Basovizza, (TS), Italy
Reinhard Denecke: Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstraße 2, D-04103 Leipzig, Germany
Marco Giorgetti: Department of Industrial Chemistry “Toso Montanari”, University of Bologna, Viale Risorgimento 4, 40136 Bologna, Italy

Energies, 2020, vol. 13, issue 15, 1-13

Abstract: Prussian Blue analogues (PBAs) are a promising class of electrode active materials for batteries. Among them, copper nitroprusside, Cu[Fe(CN) 5 NO], 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, Li x PO y Fz and Li x PF y . 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.

Keywords: copper nitroprusside; XPS; XAS; self-discharge; electrolyte degradation (search for similar items in EconPapers)
JEL-codes: Q Q0 Q4 Q40 Q41 Q42 Q43 Q47 Q48 Q49 (search for similar items in EconPapers)
Date: 2020
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