Issue 44, 2014

Sodium uptake in cell construction and subsequent in operando electrode behaviour of Prussian blue analogues, Fe[Fe(CN)6]1−x·yH2O and FeCo(CN)6

Abstract

The development of electrodes for ambient temperature sodium-ion batteries requires the study of new materials and the understanding of how crystal structure influences properties. In this study, we investigate where sodium locates in two Prussian blue analogues, Fe[Fe(CN)6]1−x·yH2O and FeCo(CN)6. The evolution of the sodium site occupancies, lattice and volume is shown during charge–discharge using in situ synchrotron X-ray powder diffraction data. Sodium insertion is found to occur in these electrodes during cell construction and therefore Fe[Fe(CN)6]1−x·yH2O and FeCo(CN)6 can be used as positive electrodes. NazFeFe(CN)6 electrodes feature higher reversible capacities relative to NazFeCo(CN)6 electrodes which can be associated with a combination of structural factors, for example, a major sodium-containing phase, ∼Na0.5FeFe(CN)6 with sodium locating either at the x = y = z = 0.25 or x = y = 0.25 and z = 0.227(11) sites and an electrochemically inactive sodium-free Fe[Fe(CN)6]1−x·yH2O phase. This study demonstrates that key questions about electrode performance and attributes in sodium-ion batteries can be addressed using time-resolved in situ synchrotron X-ray diffraction studies.

Graphical abstract: Sodium uptake in cell construction and subsequent in operando electrode behaviour of Prussian blue analogues, Fe[Fe(CN)6]1−x·yH2O and FeCo(CN)6

Supplementary files

Article information

Article type
Paper
Submitted
18 Jun 2014
Accepted
21 Jul 2014
First published
23 Jul 2014
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2014,16, 24178-24187

Author version available

Sodium uptake in cell construction and subsequent in operando electrode behaviour of Prussian blue analogues, Fe[Fe(CN)6]1−x·yH2O and FeCo(CN)6

J. C. Pramudita, S. Schmid, T. Godfrey, T. Whittle, M. Alam, T. Hanley, H. E. A. Brand and N. Sharma, Phys. Chem. Chem. Phys., 2014, 16, 24178 DOI: 10.1039/C4CP02676D

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