Decoupling Degradation at the Electrode Interfaces in Prussian White Full Cells

Abstract Prussian blue analogues for sodium‐ion battery cathodes are growing in popularity as next‐generation energy storage devices. Prussian White (PW) with formula NaxFe[Fe(CN)6]y•nH2O is leading the trend, having already been commercialized. However, capacity fade (PW/electrolyte degradation) an...

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Main Authors: Casimir Misiewicz, Alexandra E. Ulander, Tim Melin, Aram Hall, Erik J. Berg
Format: Article
Language:English
Published: Wiley-VCH 2025-05-01
Series:Advanced Materials Interfaces
Subjects:
Online Access:https://doi.org/10.1002/admi.202400854
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author Casimir Misiewicz
Alexandra E. Ulander
Tim Melin
Aram Hall
Erik J. Berg
author_facet Casimir Misiewicz
Alexandra E. Ulander
Tim Melin
Aram Hall
Erik J. Berg
author_sort Casimir Misiewicz
collection DOAJ
description Abstract Prussian blue analogues for sodium‐ion battery cathodes are growing in popularity as next‐generation energy storage devices. Prussian White (PW) with formula NaxFe[Fe(CN)6]y•nH2O is leading the trend, having already been commercialized. However, capacity fade (PW/electrolyte degradation) and safety concerns (cyanide/cyanogen release) still raise concerns. Online electrochemical mass spectrometry, supported by both operando Fourier transform infrared spectroscopy and Mössbauer spectroscopy, is herein used to analyze degradation processes in PW‐based Na‐ion full cells. Apart from the typical cell formation reactions, hydrogen is observed to evolve during cell discharge and evidenced to stem from oxidation of NaH, accumulated upon charge. Over‐oxidation of PW after full desodiation releases CN, which not only forms (CN)2 but also degrades the electrolyte. Loss of CN likely results in a nanometric (≈4 nm) surface‐reconstructed passivation layer on PW, thus inhibiting further degradation. Fundamental understanding of degradation reactions in PW full‐cells, as gathered herein, shows that the aforementioned capacity fade and safety concerns are wholly addressable and hence guides the further development of Na‐ion batteries for wider ranges of applications.
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spelling doaj-art-6211646a6adb439f8dc2da831a080d122025-08-20T03:53:51ZengWiley-VCHAdvanced Materials Interfaces2196-73502025-05-011210n/an/a10.1002/admi.202400854Decoupling Degradation at the Electrode Interfaces in Prussian White Full CellsCasimir Misiewicz0Alexandra E. Ulander1Tim Melin2Aram Hall3Erik J. Berg4Department of Chemistry Ångström Laboratory Uppsala University Box 538 Uppsala SE‐752 21 SwedenDepartment of Chemistry Ångström Laboratory Uppsala University Box 538 Uppsala SE‐752 21 SwedenDepartment of Chemistry Ångström Laboratory Uppsala University Box 538 Uppsala SE‐752 21 SwedenDepartment of Chemistry Ångström Laboratory Uppsala University Box 538 Uppsala SE‐752 21 SwedenDepartment of Chemistry Ångström Laboratory Uppsala University Box 538 Uppsala SE‐752 21 SwedenAbstract Prussian blue analogues for sodium‐ion battery cathodes are growing in popularity as next‐generation energy storage devices. Prussian White (PW) with formula NaxFe[Fe(CN)6]y•nH2O is leading the trend, having already been commercialized. However, capacity fade (PW/electrolyte degradation) and safety concerns (cyanide/cyanogen release) still raise concerns. Online electrochemical mass spectrometry, supported by both operando Fourier transform infrared spectroscopy and Mössbauer spectroscopy, is herein used to analyze degradation processes in PW‐based Na‐ion full cells. Apart from the typical cell formation reactions, hydrogen is observed to evolve during cell discharge and evidenced to stem from oxidation of NaH, accumulated upon charge. Over‐oxidation of PW after full desodiation releases CN, which not only forms (CN)2 but also degrades the electrolyte. Loss of CN likely results in a nanometric (≈4 nm) surface‐reconstructed passivation layer on PW, thus inhibiting further degradation. Fundamental understanding of degradation reactions in PW full‐cells, as gathered herein, shows that the aforementioned capacity fade and safety concerns are wholly addressable and hence guides the further development of Na‐ion batteries for wider ranges of applications.https://doi.org/10.1002/admi.202400854cyanogenonline electrochemical mass spectrometryPrussian Whitesodium‐ion batteriessolid electrolyte interphase
spellingShingle Casimir Misiewicz
Alexandra E. Ulander
Tim Melin
Aram Hall
Erik J. Berg
Decoupling Degradation at the Electrode Interfaces in Prussian White Full Cells
Advanced Materials Interfaces
cyanogen
online electrochemical mass spectrometry
Prussian White
sodium‐ion batteries
solid electrolyte interphase
title Decoupling Degradation at the Electrode Interfaces in Prussian White Full Cells
title_full Decoupling Degradation at the Electrode Interfaces in Prussian White Full Cells
title_fullStr Decoupling Degradation at the Electrode Interfaces in Prussian White Full Cells
title_full_unstemmed Decoupling Degradation at the Electrode Interfaces in Prussian White Full Cells
title_short Decoupling Degradation at the Electrode Interfaces in Prussian White Full Cells
title_sort decoupling degradation at the electrode interfaces in prussian white full cells
topic cyanogen
online electrochemical mass spectrometry
Prussian White
sodium‐ion batteries
solid electrolyte interphase
url https://doi.org/10.1002/admi.202400854
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AT aramhall decouplingdegradationattheelectrodeinterfacesinprussianwhitefullcells
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