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Galvanostatic electrodeposition of aluminium nano-rods for Li-ion three-dimensional micro-battery current collectors
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Inorganic Chemistry.ORCID iD: 0000-0001-9292-016X
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry.
2011 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 0019-4686, Vol. 56, no 9, 3203-3208 p.Article in journal (Refereed) Published
Abstract [en]

Constant current and pulsed current electrodeposition of aluminium nano-rods, for use as three-dimensional (3D) Li-ion micro-battery current collectors, have been studied using an ionic liquid electrolyte (1-ethyl-3-methylimidazolium chloride/aluminium chloride) and a template consisting of a commercial alumina membrane. It is shown that the homogeneity of the height of the rods can be improved significantly by inclusion of a short (i.e. 50 ms) potential pulse prior to the controlled current deposition step. The latter potential step increased the number of aluminium nuclei on the aluminium substrate and the best results were obtained for a potential of -0.9 V vs. Al/Al3+. The obtained nanostructured surfaces, which were characterized using electron microscopy and X-ray diffraction, consisted of parallel aligned aluminium nano-rods homogeneously distributed over the entire surface of the substrate. A narrower height distribution for the rods was obtained using a pulsed galvanostatic approach then when using a constant current, most likely due to the less favourable diffusion conditions in the latter case. The results also indicate that depletion and iR drop effects within the nano-pores result in a more homogeneous height distribution. It is concluded that the height distribution of the nano-rods is controlled by a combination of the nucleation probability in each pore at the start of the experiment, and the homogeneity of the diameters of the pores within the commercial alumina membranes employed as the electrodeposition template.

Place, publisher, year, edition, pages
2011. Vol. 56, no 9, 3203-3208 p.
Keyword [en]
Aluminium electrodeposition, Controlled current, Nano-rods, Nucleation, Three-dimensional Li-ion micro-battery
National Category
Engineering and Technology Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
URN: urn:nbn:se:uu:diva-154109DOI: 10.1016/j.electacta.2011.01.053ISI: 000290084700015OAI: oai:DiVA.org:uu-154109DiVA: diva2:419385
Available from: 2011-05-26 Created: 2011-05-26 Last updated: 2014-12-15
In thesis
1. From Current Collectors to Electrodes: Aluminium Rod Structures for Three-dimensional Li-ion Micro-battery Applications
Open this publication in new window or tab >>From Current Collectors to Electrodes: Aluminium Rod Structures for Three-dimensional Li-ion Micro-battery Applications
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The potential use of 3D aluminium nanorod structures as current collectors and negative electrodes for 3D Li-ion micro-batteries was studied based on the use of relatively simple and cost-effective electrochemical and sol-gel deposition techniques.

Aluminium rod structures were synthesised by galvanostatic electrodeposition using commercial porous membranes as templates. It was shown that the use of a short (i.e., 50 ms long) potential pulse (i.e., -0.9 V vs. Al3+/Al) applied prior to a pulsed current electrochemical deposition gave rise to homogeneous deposits with more even rod heights.  Electrophoretic and sol-gel deposition of TiO2 on the same substrates were also studied. The use of the sol-gel technique successfully resulted in a thin coating of amorphous TiO2 on the Al nanorod current collector, but with relatively small discharge capacities due to the amorphous character of the deposits. Electrophoretic deposition was, however, successful only on 2D substrates. Anodisation of titanium was used to prepare 3D TiO2 nanotube electrodes, with a nanotube length of 9 um and wall thickness of 50 nm. The electrodes displayed high and stable discharge capacities of 460 µAh/cm2 at a 0.1 C rate upon prolonged cycling with good rate capability.

The 3D aluminium nanorod structures were tested as negative electrodes for Li-ion cells and the observed capacity fading was assigned to trapping of LiAl alloy inside the aluminium electrode caused by the diffusion of lithium into the electrode, rather than to pulverisation of the aluminium rods. The capacity fading effect could, however, be eliminated by decreasing the oxidation potential limit from 3.0 to 1.0 V vs. Li+/Li. A model for the alloying and dealloying of lithium with aluminium was also proposed. Finally, a proof-of-concept for a full 3D Li-ion micro-battery with electrodes of different geometries was demonstrated. The cell comprised a positive electrode, based on LiFePO4 deposited on a carbon foam current collector, with an area gain factor an order of magnitude larger than that for the Al nanorod negative electrode. This concept facilitates the balancing of 3D Li-ion cells as the positive electrode materials generally have significant lower specific energy densities than the negative electrodes.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2014. 63 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1110
3D micro-batteries, aluminium, titanium oxide, current collectros, negative electrodes, electrodepostion, electrophoretic depostion, sol-gel synthesis
National Category
Materials Chemistry
urn:nbn:se:uu:diva-215482 (URN)978-91-554-8847-5 (ISBN)
Public defence
2014-02-28, Ångström 2001, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Available from: 2014-02-06 Created: 2014-01-14 Last updated: 2014-02-10

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