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Electrochemical fabrication and characterization of Cu/Cu2O multi-layered micro and nanorods in Li-ion batteries
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Inorganic Chemistry.
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, Inorganic Chemistry.ORCID iD: 0000-0002-4752-5491
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2015 (English)In: Nanoscale, ISSN 2040-3364, E-ISSN 2040-3372, Vol. 7, no 32, 13591-13604 p.Article in journal (Refereed) Published
Abstract [en]

Electrodes composed of freestanding nano- and microrods composed of stacked layers of copper and cuprous oxide have been fabricated using a straightforward one-step template-assisted pulsed galvanostatic electrodeposition approach. The approach provided precise control of the thickness of each individual layer of the high-aspect-ratio rods as was verified by SEM, EDS, XRD, TEM and EELS measurements. Rods with diameters of 80, 200 and 1000 nm were deposited and the influence of the template pore size on the structure and electrochemical performance of the conversion reaction based electrodes in lithium-ion batteries was investigated. The multi-layered Cu2O/Cu nano-and microrod electrodes exhibited a potential window of more than 2 V, which was ascribed to the presence of a distribution of Cu2O (and Cu, respectively) nanoparticles with different sizes and redox potentials. As approximately the same areal capacity was obtained independent of the diameter of the multi-layered rods the results demonstrate the presence of an electroactive Cu2O layer with a thickness defined by the time domain of the measurements. It is also demonstrated that while the areal capacity of the electrodes decreased dramatically when the scan rate was increased from 0.1 to 2 mV s(-1), the capacity remained practically constant when the scan rate was further increased to 100 mV s(-1). This behaviour can be explained by assuming that the capacity is limited by the lithium ion diffusion rate though the Cu2O layer generated during the oxidation step. The electrochemical performance of present type of 3-D multi-layered rods provides new insights into the lithiation and delithiation reactions taking place for conversion reaction materials such as Cu2O.

Place, publisher, year, edition, pages
2015. Vol. 7, no 32, 13591-13604 p.
National Category
Chemical Sciences
URN: urn:nbn:se:uu:diva-262013DOI: 10.1039/c5nr03472hISI: 000359234100037PubMedID: 26206712OAI: oai:DiVA.org:uu-262013DiVA: diva2:851680
Available from: 2015-09-07 Created: 2015-09-07 Last updated: 2015-11-10Bibliographically approved
In thesis
1. Insights into Electrochemical Energy Storage by use of Nanostructured Electrodes
Open this publication in new window or tab >>Insights into Electrochemical Energy Storage by use of Nanostructured Electrodes
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Template-assisted electrodeposition is a powerful technique for fabricating complex nanostructured electrodes. Through the use of pulsed-electrodeposition nanostructured electrodes of Al, Cu and Sn have been realised and subsequently coated electrochemically with V2O5, MnxO, Li, Cu2O and a polymer electrolyte. Nanorods with a multi-layered Cu2O/Cu structure have likewise been produced through electrodeposition. Nanostructured electrodes are ideal for studying electrochemical energy storage and have as such been used to investigate the electrochemistry of conversion and alloying reactions in detail.

Key properties of the Cu2O conversion reaction were found to be dependent on the particle size. Prolonged cycling was seen to induce an electrochemical milling process which reduced the particle size. This process was found to improve the cell capacity retention due to improved accessibility of the material. The redox potential at which the particles react was found to be size dependent as smaller particles reacted at lower potentials.

The Li-alloying reaction was also investigated by analysing several different alloy-forming materials. All materials exhibited a decline in capacity during cell cycling. This decline was observed to be time dependent and could as such be explained by a diffusion limited process. Moreover, the capacity losses were found to occur during partial lithiation of the electrode material leading to Li trapping in the electrode material. Li trapping was also observed for commonly used anode current collectors as the metals have some solubility for Li. Conducting boron-doped diamond electrodes were however seen to be resistant to Li diffusion and are therefore recommended as viable current collectors for anodes handling metallic lithium (i.e. Li-alloys and Li metal).

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2015. 79 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1297
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
urn:nbn:se:uu:diva-263482 (URN)978-91-554-9352-3 (ISBN)
Public defence
2015-11-20, Häggsalen, Ångströmslaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Available from: 2015-10-28 Created: 2015-09-30 Last updated: 2015-11-10

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Rehnlund, DavidValvo, MarioÅngstrom, JonasSahlberg, MartinEdström, KristinaNyholm, Leif
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