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Structural-electrochemical relations in the aqueous copper hexacyanoferrate-zinc system examined by synchrotron X-ray diffraction
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0001-9304-8975
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(English)Manuscript (preprint) (Other academic)
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 analysis with respect to the occupancies of possible Zn2+ sites suggest that the Fe(CN)6 vacancies within the CuHCF framework play an important role in the structural-electrochemical behaviour of this particular system. More specifically, it is observed that Zn2+ swaps position during electrochemical cycling, hopping between cavity sites to vacant ferricyanide sites.

National Category
Chemical Sciences
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-146262OAI: oai:DiVA.org:su-146262DiVA: diva2:1136528
Available from: 2017-08-28 Created: 2017-08-28 Last updated: 2017-08-29Bibliographically approved
In thesis
1. Prussian blue analogue copper hexacyanoferrate: Synthesis, structure characterization and its applications as battery electrode and CO2 adsorbent
Open this publication in new window or tab >>Prussian blue analogue copper hexacyanoferrate: Synthesis, structure characterization and its applications as battery electrode and CO2 adsorbent
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Prussian blue (PB) and Prussian blue analogues (PBAs) are compounds with potential applications in a large variety of fields such as gas storage, poison antidotes, electrochromism, electrochemistry and molecular magnets. The compounds are easy to synthesize, cheap, environmentally friendly and have been pursued for both fundamental research and industrial purposes. Despite the multifunctionality of PB and PBAs, they have complicated compositions, which are largely dependent on the synthesis methods and storage conditions. Thus, performing investigations on such compounds with defined composition, stoichiometry and crystal structure is essential.

This thesis has focused on synthesis and detailed structure characterization of copper hexacyanoferrate (CuHCF) via X-ray powder diffraction (XRPD), neutron powder diffraction (NPD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), inductively coupled plasma-optical emission spectroscopy (ICP-OES), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS), infrared (IR) and Raman techniques. In addition, kinetics of thermal dehydration process, CO2 adsorption and CO2 adsorption kinetics were investigated. Moreover, in operando synchrotron X-ray diffraction experiments were performed to gain insight into the structure-electrochemistry relationships in an aqueous CuHCF/Zn battery during operation.

Place, publisher, year, edition, pages
Stockholm: Materials and Environmental Chemistry, Stockholm University, 2017
Keyword
copper hexacyanoferrate, synthesis, structure refinement, thermal dehydration, CO2 adsorption, kinetic analysis, in operando synchrotron X-ray diffraction
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-146335 (URN)978-91-7649-940-5 (ISBN)978-91-7649-941-2 (ISBN)
Public defence
2017-10-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius Väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council, 2011:6512
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Manuscript.

Available from: 2017-09-18 Created: 2017-08-29 Last updated: 2017-09-14Bibliographically approved

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