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Ni3Sb4O6F6 and Its Electrochemical Behavior toward Lithium-A Combination of Conversion and Alloying Reactions
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
Stockholm Univ, Dept Mat & Environm Chem, SE-10691 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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2016 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 28, no 18, p. 6520-6527Article in journal (Refereed) Published
Abstract [en]

A group of oxohalides, where Ni3Sb4O6F6 is one example, has been investigated with respect to its electrochemical reactions toward Li+/Li. In situ and ex situ XRD measurements reveal that the original structure collapses and the material becomes amorphous upon insertion of Li at low potentials versus Li+/Li. With continued cycling, a nanocrystalline phase of NiSb, which reacts reversibly with Li, appears and steadily grows more stable. Electrochemical experiments (i.e., chronopotentiometry and cyclic voltammetry) show that multiple reactions of both conversion- and alloying-type are active in the system. High storage capacities are achieved initially but with rapid fading as a consequence of a limited reversibility of the Ni2+/Ni redox process, as shown by X-ray absorption spectroscopy of the first discharge/charge cycle. Stable cycling can be achieved by optimizing the cutoff potentials (i.e., excluding poorly reversible reactions at high and low voltages, respectively), yielding long-term cycling with a practical gravimetric capacity of similar to 200 mAh g(-1).

Place, publisher, year, edition, pages
2016. Vol. 28, no 18, p. 6520-6527
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-307284DOI: 10.1021/acs.chemmater.6b01914ISI: 000384399000015OAI: oai:DiVA.org:uu-307284DiVA, id: diva2:1046103
Funder
Swedish Research Council, 2011-6512
Available from: 2016-11-11 Created: 2016-11-11 Last updated: 2017-11-29Bibliographically 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
Keyword
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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