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Electrodeposition and electrochemical characterisation of thick and thin coatings of Sb and Sb/Sb2O3 particles for Li-ion battery anodes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
2007 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 53, no 3, 1062-1073 p.Article in journal (Refereed) Published
Abstract [en]

The possibilities to electrodeposit thick coatings composed of nanoparticles of Sb and Sb2O3 for use as high-capacity anode materials in Li-ion batteries have been investigated. It is demonstrated that the stability of the coatings depends on their Sb2O3 concentrations as well as microstructure. The electrodeposition reactions in electrolytes with different pH and buffer capacities were studied using chronopotentiometry and electrochemical quartz crystal microbalance measurements. The obtained deposits, which were characterised with XRD and SEM, were also tested as anode materials in Li-ion batteries. The influence of the pH and buffer capacity of the deposition solution on the composition and particle size of the deposits were studied and it is concluded that depositions from a poorly buffered solution of antimony-tartrate give rise to good anode materials due to the inclusion of precipitated Sb2O3 nanoparticles in the Sb coatings. Depositions under conditions yielding pure Sb coatings give rise to deposits composed of large crystalline particles with poor anode stabilities. The presence of a plateau at about 0.8V versus Li+/Li due to SEI forming reactions and the origin of another plateau at about 0.4 V versus Li+/Li seen during the lithiation of thin Sb coatings are also discussed. It is demonstrated that the 0.4 V plateau is present for Sb coatings for which the (0 1 2) peak is the main peak in the XRD diffractogram.

Place, publisher, year, edition, pages
2007. Vol. 53, no 3, 1062-1073 p.
Keyword [en]
Transition metal, Lithion ion batteries, Electrical characteristic, Morphology, Surface structure, Secondary cell, Electrochemical reaction, Specific capacity, Reaction mechanism, Electrode material, Nanoparticle, Anode, Nickel, Antimony Oxides, Thin film, Scanning electron microscopy, X ray diffraction, Antimony, Electrodeposition
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-96859DOI: 10.1016/j.electacta.2007.02.009ISI: 000251305300004OAI: oai:DiVA.org:uu-96859DiVA: diva2:171580
Available from: 2008-03-19 Created: 2008-03-19 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Insights into Stability Aspects of Novel Negative Electrodes for Li-ion Batteries
Open this publication in new window or tab >>Insights into Stability Aspects of Novel Negative Electrodes for Li-ion Batteries
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Demands for high energy-density batteries have sharpened with the increased use of portable electronic devices, as has the focus global warming is now placing on the need for electric and electric-hybrid vehicles. Li-ion battery technology is superior to other rechargeable battery technologies in both energy- and power-density. A remaining challenge, however, is to find an alternative candidate to graphite as the commercial anode. Several metals can store more lithium than graphite, e.g., Al, Sn, Si and Sb. The main problem is the large volume changes that these metals undergo during the lithiation process, leading to degradation and pulverization of the anode with resulting limitations in cycle-life.

The Li-ion battery is studied in this thesis with the goal of better understanding the critical parameters determining high and stable electrochemical performance when using a metal or a metal-alloy anode. Various antimony-containing systems will be presented. These represent different routes to circumvent the problems caused by volume change. Sb-compounds exhibit a high lithium storage capability. At most, three Li-ions can be stored per Sb atom, leading to a theoretical gravimetric capacity of 660 mAh/g. Model systems with stepwise increasing complexity have been designed to better understand the factors influencing lithium insertion/extraction.

It is demonstrated that the microstructure of the anode material is crucial to stable cycling performance and high reversibility. The relative importance of the various factors controlling stability, such as particle-size, oxide content and morphology, varies strongly with the type of system studied. The cycling performance of pure Sb is improved dramatically by incorporating a second component, Sb2O3. With a critical oxide concentration of ~25%, a stable capacity close to the theoretical value of 770 mAh/g is obtained for over 50 cycles. Cu2Sb shows stable cycling performance in the absence of oxide. Cu9Sb2 has been presented for the first time as an anode material in a Li-ion battery context. Studies of the Solid Electrolyte Interphase (SEI) formed on AlSb composite electrodes show an SEI layer thinner than graphite, and with a clearly dynamic character.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2008. 62 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 405
Keyword
Inorganic chemistry, Li-ion batteries, anode materials, Sb, Cu2Sb, electrodeposition, Oorganisk kemi
Identifiers
urn:nbn:se:uu:diva-8537 (URN)978-91-554-7124-8 (ISBN)
Public defence
2008-04-11, Polhemsalen, Ångströmslaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2008-03-19 Created: 2008-03-19 Last updated: 2010-03-05Bibliographically approved
2. Electrochemical Deposition of Nanostructured Metal/Metal-Oxide Coatings
Open this publication in new window or tab >>Electrochemical Deposition of Nanostructured Metal/Metal-Oxide Coatings
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Electrochemical deposition finds applications in the electronics- and protective coating industries. The technique is a versatile tool for the synthesis of alloys and thin films. Knowledge of the fundamental aspects of the electrode processes enables the design of nanostructured materials. In this thesis, electrodeposition processes in solutions containing metal ion complexes were studied and new methods for the preparation of metal/metal-oxide coatings were developed and evaluated.

Metal/metal oxide coatings were electrodeposited from aqueous solutions containing metal complexes of hydroxycarboxylic acids under reducing conditions. The mass changes of the working electrode were monitored in-situ with the electrochemical quartz crystal microbalance (EQCM) technique and ellipsometry was used to detect the formation of Cu2O. The coatings were further characterized with XRD, XPS, SEM, TEM, and Raman spectroscopy. Electrochemical methods, including reduction of Sb/Sb2O3 in an organic electrolyte, were also used to study the properties of the deposited materials.

Nanostructured coatings of Cu/Cu2O were obtained during spontaneous potential or current oscillations in alkaline Cu(II)-citrate solutions. The oscillations were due to local pH variations induced by a subsequent chemical step and comproportionation between Cu and Cu2+. Well-defined layers of Cu and Cu2O could be prepared by a galvanostatic pulsing technique, allowing independently controlled thickness of several hundred nanometers. Coatings, containing Sb and co-deposited, nanograins of Sb2O3, with a thickness of up to 200 nm were prepared from poorly buffered Sb(III)-tartrate solutions. Galvanostatic cycling showed that the latter material could be reversibly charged and discharged in a Li-ion battery for more than 50 cycles with a capacity of 660 mAh/g.

The results show that precipitations of metal oxides can occur due to local pH increases during electrochemical deposition from metal complexes with ligands containing hydroxyl groups. The ability to deposit metal oxides using cathodic deposition relies on a sufficiently slow reduction of the oxide.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2007. 54 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 336
Keyword
Inorganic chemistry, electrochemical deposition, local pH, Cu2O, Sb2O3, complex, EQCM, reduction, Oorganisk kemi
Identifiers
urn:nbn:se:uu:diva-8186 (URN)978-91-554-6956-6 (ISBN)
Public defence
2007-09-28, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 14:00
Opponent
Supervisors
Available from: 2007-09-07 Created: 2007-09-07 Last updated: 2011-03-25Bibliographically approved

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