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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.
Stockholm University, Stockholm, Sweden.
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, p. 146-153Article 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
2017. Vol. 369, p. 146-153
Keywords [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.2017.09.079ISI: 000413799900018OAI: oai:DiVA.org:uu-334062DiVA, id: diva2:1158591
Funder
Swedish Research Council, 2011-6512Swedish Research Council Formas, 245-2014-668Available from: 2017-11-20 Created: 2017-11-20 Last updated: 2018-02-05Bibliographically approved
In thesis
1. Structural and Electrochemical Relations in Electrode Materials for Rechargeable Batteries
Open this publication in new window or tab >>Structural and Electrochemical Relations in Electrode Materials for Rechargeable Batteries
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Rechargeable batteries have already conquered the market of portable electronics (i.e., mobile phones and laptops) and are set to further enable the large-scale deployment of electric vehicles and hybrid electric vehicles in a not too distant future. In this context, a deeper understanding of the fundamental processes governing the electrochemical behavior of electrode materials for batteries is required for further development of these applications. The aims of the work described in this thesis have been to investigate how electrochemical properties and structural properties of novel electrode materials relate to each other. In this sense, electrochemical characterization, structural analysis using XRD and their combined simultaneous use via in operando XRD experiments have played a crucial part.

The investigations showed that: Two oxohalides, Ni3Sb4O6F6 and Mn2Sb3O6Cl, react with Li-ions in a complex manner involving different types of reaction mechanisms at low voltages in Li half cells. In operando XRD show that both of these materials are reduced in a conversion reaction via an in situ formation of nanocomposites, which proceed to react reversibly with Li-ions in a combination of alloying and conversion reactions.

Carbon-coated Na2Mn2Si2O7 was synthesized and characterized as a possible positive electrode material for non-aqueous Na-ion batteries. DFT calculations point to a structural origin of the modest electrochemical behavior of this material. It is suggested that structural rearrangements upon desodiation are associated with large overpotentials.

It is demonstrated via an in operando synchrotron XRD study that Fe(CN)6 vacancies in copper hexacyanoferrate (CuHCF) play an important role in the electrochemical behavior toward Zn2+ in an aqueous CuHCF/Zn cell. Furthermore, manganese hexacyanomanganate (MnHCM) is shown to react reversibly with Li+, Na+ and K+ in non-aqueous alkali metal half cells. In contrast to CuHCF, which is a zero-strain material, MnHCM undergoes a series of structural transitions (from monoclinic to cubic) during electrochemical cycling.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. p. 87
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1599
Keywords
batteries, electrochemical energy storage, oxohalides, conversion, alloy, pyrosilicate, CuHCF, MnHCM, XRD, XANES, in operando
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-334078 (URN)978-91-513-0155-6 (ISBN)
Public defence
2018-01-12, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2017-12-21 Created: 2017-11-20 Last updated: 2018-03-08

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Renman, ViktorValvo, MarioGómez, Cesar PayGustafsson, Torbjörn

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