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Insights into Electrochemical Energy Storage by use of Nanostructured Electrodes
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Inorganic Chemistry.ORCID iD: 0000-0003-2394-287X
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.
Series
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
Identifiers
URN: urn:nbn:se:uu:diva-263482ISBN: 978-91-554-9352-3 (print)OAI: oai:DiVA.org:uu-263482DiVA: diva2:858070
Public defence
2015-11-20, Häggsalen, Ångströmslaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2015-10-28 Created: 2015-09-30 Last updated: 2015-11-10
List of papers
1. Electrodeposition of Vanadium Oxide/Manganese Oxide Hybrid Thin Films on Nanostructured Aluminum Substrates
Open this publication in new window or tab >>Electrodeposition of Vanadium Oxide/Manganese Oxide Hybrid Thin Films on Nanostructured Aluminum Substrates
2014 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 161, no 10, D515-D521 p.Article in journal (Refereed) Published
Abstract [en]

Electrodeposition of functional coatings on aluminum electrodes in aqueous solutions often is impeded by the corrosion of aluminum. In the present work it is demonstrated that electrodeposition of vanadium, oxide films on nanostructured aluminum substrates can be achieved in acidic electrolytes employing a novel strategy in which a thin interspacing layer of manganese oxide is first electrodeposited on aluminum microrod substrates. Such deposited films, which were studied using SEM, XPS, XRD, and surface enhances Raman scattering as well as chronopotentiometry, are shown to comprise a mixture of vanadium oxidation states (i.e. IV and V). As this all-electrochemical approach circumvents the problems associated with aluminum corrosion, the approach provides new possibilities for the electrochemical coating of nanostructured Al substrates with functional layers of metal oxides. The latter significantly facilitates the development of new procedures for the manufacturing of three-dimensional aluminum based electrodes for lithium ion microbatteries. (C) The Author(s) 2014. Published by ECS. All rights reserved.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-233126 (URN)10.1149/2.0511410jes (DOI)000341217500062 ()
Available from: 2014-09-29 Created: 2014-09-29 Last updated: 2017-12-05Bibliographically approved
2. The impact of size effects on the electrochemical behaviour of Cu2O-coated Cu nanopillars for advanced Li-ion microbatteries
Open this publication in new window or tab >>The impact of size effects on the electrochemical behaviour of Cu2O-coated Cu nanopillars for advanced Li-ion microbatteries
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2014 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 2, no 25, 9574-9586 p.Article in journal (Refereed) Published
Abstract [en]

The generation of a distribution of nanoparticles upon conversion reaction of thin Cu2O layers is demonstrated to produce a wide electrochemical potential window, as well as a distinctive capacity increase in large area three-dimensional electrodes. Cu nanopillars with a 10-15 nm Cu2O coating containing traces of nanocrystattine Fe2O3 yield capacities up to 0.265 mA h cm(-2) (at 61 mA g(-1)), excellent cycling for more than 300 cycles and an electroactive potential window larger than 2 V. due to the size effects caused by the various Cu/Cu2O nanopartictes formed during conversion/deconversion. These 3D Li-ion battery electrodes based on etectrodeposited Cu nanopillars spontaneously coated with a Cu2O layer are compatible with current densities of 16 A g(-1) (i.e. 61 C rates) after aerosol-assisted infiltration with an iron acetate solution followed by low-temperature pyrolysis. The capacity of the composite material increases by 67% during 390 cycles due to the growth of the electroactive area during the electrochemical milling of Cu2O forced by its repeated conversion/de-conversion. The latter generates a distribution of nanoparticles with different sizes and redox potentials, which explains the broad potential window, as well as the significant capacity contribution from double layer charging. These 3D electrodes should be well-suited for Li-ion microbatteries and Li-ion batteries in general, since they combine high capacities per footprint area with excellent power capabilities. More importantly, such electrodes grant access to fundamental understanding of the electrochemical behaviour of these active materials providing new insights into both conversion mechanisms and nanostructured interfaces more in general.

National Category
Other Chemistry Topics Other Physics Topics
Identifiers
urn:nbn:se:uu:diva-228953 (URN)10.1039/c4ta01361a (DOI)000337774100019 ()
Available from: 2014-07-25 Created: 2014-07-24 Last updated: 2015-11-10
3. Electrodeposition of thin poly(propylene glycol) acrylate electrolytes on 3D-nanopillar electrodes
Open this publication in new window or tab >>Electrodeposition of thin poly(propylene glycol) acrylate electrolytes on 3D-nanopillar electrodes
2014 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 137, 320-327 p.Article in journal (Refereed) Published
Keyword
3D-microbattery, Electropolymerization, Polymer electrolyte, Cu nano-pillars
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-233516 (URN)10.1016/j.electacta.2014.06.008 (DOI)000341462500040 ()
Available from: 2014-10-06 Created: 2014-10-06 Last updated: 2017-12-05
4. Electrochemical fabrication and characterization of Cu/Cu2O multi-layered micro and nanorods in Li-ion batteries
Open this publication in new window or tab >>Electrochemical fabrication and characterization of Cu/Cu2O multi-layered micro and nanorods in Li-ion batteries
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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.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-262013 (URN)10.1039/c5nr03472h (DOI)000359234100037 ()26206712 (PubMedID)
Available from: 2015-09-07 Created: 2015-09-07 Last updated: 2017-12-04Bibliographically approved
5. Microbatteries based on 3D Li and Cu2O coated Cu nanorods
Open this publication in new window or tab >>Microbatteries based on 3D Li and Cu2O coated Cu nanorods
(English)Manuscript (preprint) (Other academic)
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-263480 (URN)
Available from: 2015-09-30 Created: 2015-09-30 Last updated: 2015-11-10
6. Diffusion Controlled Trapping of Elemental Lithium in Alloy forming Materials and Current Collectors for Lithium based Batteries
Open this publication in new window or tab >>Diffusion Controlled Trapping of Elemental Lithium in Alloy forming Materials and Current Collectors for Lithium based Batteries
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(English)Manuscript (preprint) (Other academic)
Keyword
Lithium-ion battery, lithium diffusion, tin, silicon, alloys, trapping
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-263478 (URN)
Available from: 2015-09-30 Created: 2015-09-30 Last updated: 2015-11-10

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