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Electrodeposited Sb and Sb/Sb2O3 nanoparticle coatings as anode materials for Li-ion batteries
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.
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2007 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 19, no 5, 1170-1180 p.Article in journal (Refereed) Published
Abstract [en]

Galvanostatically electrodeposited coatings of pure Sb or co-deposited Sb and Sb2O3 nanoparticles, prepared from antimony tartrate solutions, were studied as anode materials in Li-ion batteries. It is demonstrated that the co-deposition of 20-25% (w/w) Sb2O3 results from a local pH increase at the cathode (due to protonation of liberated tartrate) in poorly buffered solutions. This causes precipitation of Sb2O3 nanoparticles and inclusion of some of the particles in the deposit where they become coated with a protecting layer of Sb. Chronopotentiometric cycling of the deposits, which also were characterized using, e.g., SEM, TEM, and XRD, clearly showed that the Sb2O3-containing deposits were superior as anode materials. While the Sb/Sb2O3 coatings exhibited a specific capacity close to the Sb theoretical value of 660 mA·h·g -1 during more than 50 cycles, the capacity for the Sb coatings gradually decreased to about 250 mA·h·g-1. This indicates that the influence of the significant volume changes present upon the formation and oxidation of Li3Sb was much smaller for the Sb/Sb2O3 nanoparticle coatings. The improved performance can be explained by significant formation of Sb2O3 during the reoxidation, the presence of smaller Sb particles in the Sb/Sb2O3 coatings, and the formation of buffering nanoparticles of Li2O in a matrix of Sb during the first reduction cycle for the Sb/Sb2O3 deposits.

Place, publisher, year, edition, pages
2007. Vol. 19, no 5, 1170-1180 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-96156DOI: 10.1021/cm0624769ISI: 000244467800034OAI: oai:DiVA.org:uu-96156DiVA: diva2:170634
Available from: 2007-09-07 Created: 2007-09-07 Last updated: 2017-12-14Bibliographically approved
In thesis
1. 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
2. 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

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