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Structural-electrochemical relations in the aqueous copper hexacyanoferrate-zinc system examined by synchrotron X-ray diffraction
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
(Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK))
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
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2017 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 369, 146-153 p.Article in journal (Refereed) Published
Abstract [en]

The storage process of Zn2+ in the Prussian blue analogue (PBA) copper hexacyanoferrate (Cu[Fe(CN)6]2/3-nH2O - CuHCF) framework structure in a context of rechargeable aqueous batteries is examined by means of in operando synchrotron X-ray diffraction. Via sequential unit-cell parameter refinements of time-resolved diffraction data, it is revealed that the step-profile of the cell output voltage curves during repeated electrochemical insertion and removal of Zn2+ in the CuHCF host structure is associated with a non-linear contraction and expansion of the unit-cell in the range 0.36 < x < 1.32 for Znx/3Cu[Fe(CN)6]2/3-nH2O. For a high insertion cation content there is no apparent change in the unit-cell contraction. Furthermore, a structural analysiswith respect to the occupancies of possible Zn2+ sites suggests that the Fe(CN)6 vacancies within the CuHCF framework play an important role in the structural-electrochemical behavior of this particular system. More specifically, it is observed that Zn2+ swaps position during electrochemical cycling, hopping between cavity sites to vacant ferricyanide sites.

Place, publisher, year, edition, pages
Elsevier, 2017. Vol. 369, 146-153 p.
Keyword [en]
Prussian blue analogues, Copper hexacyanoferrate, Zinc, Aqueous electrochemical energy storage, In operando X-ray diffraction, Synchrotron radiation
National Category
Inorganic Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-334062DOI: 10.1016/j.jpowsour.2017.09.079OAI: oai:DiVA.org:uu-334062DiVA: diva2:1158591
Available from: 2017-11-20 Created: 2017-11-20 Last updated: 2017-11-20
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