The emerging energy demand and need to develop sustainable energy storage systems have drawn extensive attention to fundamental and applied research. Anion redox processes were proposed in cathodic materials in addition to traditional transition metal redox to boost the specific capacity and the electrochemical performance. Alternatively, copper nitroprusside (CuNP) features an electroactive nitrosyl ligand alongside the two structural metals (Fe, Cu), representing an alternative to anion redox in layered oxides. Here, a deep structural investigation is carried out on CuNP by complementing the long-range order sensitivity of X-ray diffraction (XRD) and the local atomic probe of X-ray absorption (XAS). Two different CuNP materials are studied, the hydrated and dehydrated forms. A new phase for hydrated CuNP not reported in the literature is solved, and Rietveld refined. The XAS spectra of the two materials at the Cu and Fe K-edges show a similar yet different atomic environment. The extended XAS spectra (EXAFS) analysis is accomplished by considering threeand four-body terms due to the high collinearity of the atomic chains and gives accurate insight into the first-, second-, and third-shell interatomic distances. Both materials are mounted in Li-ion and Na-ion cells to explore the link between structure and electrochemical performance. As revealed by the charge/discharge cycles, the cyclability in Na-ion cells is negatively affected by interstitial water. The similarity in the local environment and the electrochemical differences suggest a long-range structural dependence on the electrochemical performance.

Cross-investigation on copper nitroprusside: Combining XRD and XAS for in-depth structural insights / Mullaliu A.; Aquilanti G.; Plaisier J.R.; Giorgetti M.. - In: CONDENSED MATTER. - ISSN 2410-3896. - STAMPA. - 6:3(2021), pp. 27.1-27.11. [10.3390/condmat6030027]

Cross-investigation on copper nitroprusside: Combining XRD and XAS for in-depth structural insights

Mullaliu A.;Giorgetti M.
2021

Abstract

The emerging energy demand and need to develop sustainable energy storage systems have drawn extensive attention to fundamental and applied research. Anion redox processes were proposed in cathodic materials in addition to traditional transition metal redox to boost the specific capacity and the electrochemical performance. Alternatively, copper nitroprusside (CuNP) features an electroactive nitrosyl ligand alongside the two structural metals (Fe, Cu), representing an alternative to anion redox in layered oxides. Here, a deep structural investigation is carried out on CuNP by complementing the long-range order sensitivity of X-ray diffraction (XRD) and the local atomic probe of X-ray absorption (XAS). Two different CuNP materials are studied, the hydrated and dehydrated forms. A new phase for hydrated CuNP not reported in the literature is solved, and Rietveld refined. The XAS spectra of the two materials at the Cu and Fe K-edges show a similar yet different atomic environment. The extended XAS spectra (EXAFS) analysis is accomplished by considering threeand four-body terms due to the high collinearity of the atomic chains and gives accurate insight into the first-, second-, and third-shell interatomic distances. Both materials are mounted in Li-ion and Na-ion cells to explore the link between structure and electrochemical performance. As revealed by the charge/discharge cycles, the cyclability in Na-ion cells is negatively affected by interstitial water. The similarity in the local environment and the electrochemical differences suggest a long-range structural dependence on the electrochemical performance.
2021
Cross-investigation on copper nitroprusside: Combining XRD and XAS for in-depth structural insights / Mullaliu A.; Aquilanti G.; Plaisier J.R.; Giorgetti M.. - In: CONDENSED MATTER. - ISSN 2410-3896. - STAMPA. - 6:3(2021), pp. 27.1-27.11. [10.3390/condmat6030027]
Mullaliu A.; Aquilanti G.; Plaisier J.R.; Giorgetti M.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/845503
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