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From Current Collectors to Electrodes: Aluminium Rod Structures for Three-dimensional Li-ion Micro-battery Applications
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
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.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1110
Keyword [en]
3D micro-batteries, aluminium, titanium oxide, current collectros, negative electrodes, electrodepostion, electrophoretic depostion, sol-gel synthesis
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-215482ISBN: 978-91-554-8847-5 (print)OAI: oai:DiVA.org:uu-215482DiVA: diva2:687433
Public defence
2014-02-28, Ångström 2001, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2014-02-06 Created: 2014-01-14 Last updated: 2014-02-10
List of papers
1. Galvanostatic electrodeposition of aluminium nano-rods for Li-ion three-dimensional micro-battery current collectors
Open this publication in new window or tab >>Galvanostatic electrodeposition of aluminium nano-rods for Li-ion three-dimensional micro-battery current collectors
2011 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, 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.

Keyword
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
Identifiers
urn:nbn:se:uu:diva-154109 (URN)10.1016/j.electacta.2011.01.053 (DOI)000290084700015 ()
Available from: 2011-05-26 Created: 2011-05-26 Last updated: 2017-12-11
2. On the Electrophoretic and Sol-gel Depostion of Active Materials on Aluminium Rod Current Collectors for Three-dimensional Li-ion Micro-batteries
Open this publication in new window or tab >>On the Electrophoretic and Sol-gel Depostion of Active Materials on Aluminium Rod Current Collectors for Three-dimensional Li-ion Micro-batteries
(English)Article in journal (Refereed) Submitted
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-215444 (URN)
Available from: 2014-01-14 Created: 2014-01-14 Last updated: 2014-12-15
3. High energy and power density TiO2 nanotube electrodes for 3D Li-ion microbatteries
Open this publication in new window or tab >>High energy and power density TiO2 nanotube electrodes for 3D Li-ion microbatteries
Show others...
2013 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 1, no 28, 8160-8169 p.Article in journal (Refereed) Published
Abstract [en]

Highly ordered anodic TiO2 nanotube arrays with a tube length of 9 [small mu ]m are shown to provide areal capacities of 0.24 mA h cm-2 (i.e. 96 mA h g-1) at a charge/discharge current density of 2.5 mA cm-2 (corresponding to a rate of 5 C) and 0.46 mA h cm-2 (i.e. 184 mA h g-1) at 0.05 mA cm-2, when used as 3D free-standing anodes in Li-ion microbatteries. The present nanotube electrodes, which could be cycled for 500 cycles with only 6% loss of capacity, exhibited significantly higher energy and power densities, as well as an excellent cycling stability compared to previously reported TiO2-based Li-ion microbattery electrodes. The influence of parameters such as ordering, geometry and crystallinity of the nanotubes on the microbattery performance was investigated. A two-step anodization process followed by annealing of the nanotubes was found to yield the best microbattery performance. It is also demonstrated that the rate capability of the electrode depends mainly on the rate of the structural rearrangements associated with the lithiation/delithiation reaction and that the areal capacity at various charge/discharge rates can be increased by increasing the tube wall thickness or the length of the nanotubes, up to 0.6 mA h cm-2 for 100 cycles.

National Category
Nano Technology
Research subject
Materials Science
Identifiers
urn:nbn:se:uu:diva-202840 (URN)10.1039/C3TA11273J (DOI)000320876000012 ()
Funder
Swedish Research Council
Available from: 2013-06-27 Created: 2013-06-27 Last updated: 2014-12-15
4. On the origin of the capacity fading for aluminium negative electrodes in Li-ion batteries
Open this publication in new window or tab >>On the origin of the capacity fading for aluminium negative electrodes in Li-ion batteries
2014 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 269, 266-273 p.Article in journal (Refereed) Published
Abstract [en]

The origin of the capacity loss for aluminium negative electrodes in Li-ion batteries has been studied for electrodeposited aluminium nanorod electrodes coated with Al2O3 layers of different thicknesses (i.e. a native oxide layer, 30 and 60 nm) mainly employing pouch cell voltammetric cycling versus metallic lithium. Whereas the capacity decreased continuously during cycling between 0.1 and 3 V vs. Li+/Li, good cycling stability was obtained when the cycling was carried out between 0.1 and 1 V vs. Li+/Li. Since no significant dependence of the cycling stability on the thickness of the alumina layer was found in any of the experiments, the observed loss of capacity is unlikely to have been caused by volume expansion effects. The latter is further supported by the finding that the capacity (obtained when cycling between 0.1 and 3 V vs. Li+/Li) decreased linearly with the inverse of the square root of the cycling time, indicating that the capacity loss was due to the loss of lithium as a result of lithium diffusion into the bulk of the aluminium electrodes. The latter is explained based on a lithium-aluminium alloying and dealloying model which complements previously published models.

National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-215446 (URN)10.1016/j.jpowsour.2014.06.118 (DOI)000340975200036 ()
Funder
Swedish Research Council, 2011-3506
Available from: 2014-01-14 Created: 2014-01-14 Last updated: 2017-12-06
5. A Full 3D Li-ion Microbattery with Different Electrode Geometries
Open this publication in new window or tab >>A Full 3D Li-ion Microbattery with Different Electrode Geometries
(English)Article in journal (Refereed) Submitted
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-215447 (URN)
Available from: 2014-01-14 Created: 2014-01-14 Last updated: 2014-12-15

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