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Physical Vapor Deposition of Yttria-Stabilized Zirconia and Gadolinia-Doped Ceria Thin Films for Fuel Cell Applications
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
2012 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, reactive sputter deposition of yttria-stabilized zirconia (YSZ) and cerium gadolinium oxide (CGO) thin films for solid oxide fuel cell (SOFC) applications have been studied. All films have been deposited under industrial conditions.

YSZ films were deposited on silicon wafers as well as commercial NiO-YSZ fuel cell anodes. The texture, morphology, and composition of the deposited films were investigated with respect to deposition parameters such as bias voltage which was identified as a key parameter to tailor the texture of the film and promote less columnar coatings when depositing on Si. In contrast, films grown on NiO-YSZ fuel cell anodes were seen to be randomly orientated when deposited at low substrate bias voltages. When the bias voltage was increased the film took over the orientation of underlying substrate due to substrate template effects. The deposited coatings were found to be homogeneous large areas within the coating zone, which is highly important for industrial applications.

The performance of sputtered CGO thin films as diffusion barriers for stopping Sr diffusion between SOFC cathodes and electrolytes was also studied. This was done by introducing the sputtered CGO films in a metal-based SOFC setup. The performance depended on the density of the barrier layer, signifying that Sr diffusion and SrZrO3 formation is an issue. Area specific resistances down to 0.27 Ωcm2, corresponding to a maximum power density up to 1.14 W cm−2 at 650 °C could be obtained with sputtered CGO barrier layers in combination with Sr-doped lanthanum cobalt oxide cathodes which is a significant improvement compared conventional ceramic SOFCs.

The diffusion mechanism of Sr through sputtered CGO films was investigated. For this purpose, a model system simulating a SOFC was prepared by depositing CGO and YSZ on cathode material. This setup allowed observation of Sr diffusion by observing SrZrO3 formation using X-ray diffraction while annealing. Electron microscopy was subsequently performed to confirm the results. It was found that Sr diffused along column/grain boundaries in the CGO films but by modifying the film thickness and microstructure the breaking temperature of the barrier could be increased.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2012. , p. 40
Series
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1552
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-84611Local ID: LIU-TEK-LIC-2012:37ISBN: 978-91-7519-767-8 (print)OAI: oai:DiVA.org:liu-84611DiVA, id: diva2:560665
Presentation
2012-11-12, Planck, Fysikhusete, Campus Valla, Linköpings universitet, Linköping, 10:15 (Swedish)
Opponent
Supervisors
Available from: 2012-10-15 Created: 2012-10-15 Last updated: 2019-12-19Bibliographically approved
List of papers
1. Reactive magnetron sputtering of uniform yttria-stabilized zirconia coatings in an industrial setup
Open this publication in new window or tab >>Reactive magnetron sputtering of uniform yttria-stabilized zirconia coatings in an industrial setup
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2012 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 206, no 19-20, p. 4126-4131Article in journal (Refereed) Published
Abstract [en]

Yttria-stabilized zirconia (YSZ) thin films were deposited by reactive magnetron sputtering in an industrial scale setup on silicon wafers as well as commercial NiO-YSZ fuel cell anodes. The texture, morphology, and composition of the deposited films were investigated as a function of deposition parameters. Homogeneous coatings could be deposited over large areas within the coating zone, which is important for industrial applications. The use of substrate bias during film growth was identified as a key parameter to promote less columnar coatings and made it possible to tailor the texture of films deposited on Si. Bias voltages less than= - 40V resulted in highly less than 200 greater than textured YSZ films, intermediate bias voltages of - 50 V to - 70 V in less than 220 greater than textured films and high bias voltages (greater than= - 90 V) in a mixed orientation. In contrast, films grown on NiO-YSZ were seen to be randomly orientated when deposited at substrate bias voltages less than= - 30 V. When bias was further increased the film took over the orientation of underlying substrate due to substrate template effects.

Place, publisher, year, edition, pages
Elsevier, 2012
Keywords
Physical vapor deposition (PVD); Solid oxide fuel cell (SOFC); X-ray diffraction (XRD); Electron microscopy; Elastic recoil detection analysis (ERDA)
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-79708 (URN)10.1016/j.surfcoat.2012.04.007 (DOI)000305662400043 ()
Available from: 2012-08-13 Created: 2012-08-13 Last updated: 2017-12-07
2. High performance metal-supported solid oxide fuel cells with Gd-doped ceria barrier layers
Open this publication in new window or tab >>High performance metal-supported solid oxide fuel cells with Gd-doped ceria barrier layers
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2011 (English)In: Journal of Power Sources, ISSN 0378-7753, E-ISSN 1873-2755, Vol. 196, no 22, p. 9459-9466Article in journal (Refereed) Published
Abstract [en]

Metal-supported solid oxide fuel cells are believed to have commercial advantages compared to conventional anode (Ni-YSZ) supported cells, with the metal-supported cells having lower material costs, increased tolerance to mechanical and thermal stresses, and lower operational temperatures. The implementation of a metallic support has been challenged by the need to revise the cell fabrication route, as well as electrode microstructures and material choices, to compete with the energy output and stability of full ceramic cells. less thanbrgreater than less thanbrgreater thanThe metal-supported SOFC design developed at Riso DTU has been improved, and an electrochemical performance beyond the state-of-the-art anode-supported SOFC is demonstrated possible, by introducing a CGO barrier layer in combination with Sr-doped lanthanum cobalt oxide (LSC) cathode. Area specific resistances (ASR) down to 0.27 Omega cm(2), corresponding to a maximum power density of 1.14 W cm(-2) at 650 degrees C and 0.6 V. were obtained on cells with barrier layers fabricated by magnetron sputtering. The performance is dependent on the density of the barrier layer, indicating Sr(2+) diffusion is occurring at the intermediate SOFC temperatures. The optimized design further demonstrate improved durability with steady degradation rates of 0.9% kh(-1) in cell voltage for up to 3000 h galvanostatic testing at 650 degrees C and 0.25 A cm(-2).

Place, publisher, year, edition, pages
Elsevier, 2011
Keywords
SOFC, Metal-supported, Barrier layer, Magnetron sputtering, Durability
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-71631 (URN)10.1016/j.jpowsour.2011.07.014 (DOI)000295602400048 ()
Note

Funding Agencies|Topsoe Fuel Cell A/S||Danish National Advanced Technology Foundation||EU|FP7-211940 (METSOFC)|NordForsk|9346|

Available from: 2011-10-27 Created: 2011-10-27 Last updated: 2017-12-08
3. Strontium diffusion in magnetron sputtered gadolinia-doped ceria thin film barrier coatings for solid oxide fuel cells
Open this publication in new window or tab >>Strontium diffusion in magnetron sputtered gadolinia-doped ceria thin film barrier coatings for solid oxide fuel cells
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2013 (English)In: Advanced Energy Materials, E-ISSN 1614-6840, Vol. 3, no 7, p. 923-929Article in journal (Refereed) Published
Abstract [en]

Strontium (Sr) diffusion in magnetron sputtered gadolinia-doped ceria (CGO) thin films is investigated. For this purpose, a model system consisting of a screen printed (La,Sr)(Co,Fe)O3−δ (LSCF) layer, and thin films of CGO and yttria-stabilized zirconia (YSZ) is prepared to simulate a solid oxide fuel cell. This setup allows observation of Sr diffusion by observing SrZrO3 formation using X-ray diffraction while annealing. Subsequent electron microscopy confirms the results. This approach presents a simple method for assessing the quality of CGO barriers without the need for a complete fuel cell test setup. CGO films with thicknesses ranging from 250 nm to 1.2 μm are tested at temperatures from 850 °C to 950 °C which yields an in-depth understanding of Sr diffusion through CGO thin films that may be of high scientific and technical interest for implementation of novel fuel cell materials. Sr is found to diffuse along column/grain boundaries in the CGO films but by modifying the film thickness and microstructure the breaking temperature of the barrier can be increased.

Place, publisher, year, edition, pages
John Wiley & Sons, 2013
Keywords
Ce0.9Gd0.1O2−δ; CGO; GDC; Sr diffusion; X-ray diffraction
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-84610 (URN)10.1002/aenm.201300003 (DOI)000327698200015 ()
Note

On the day of the defence date the status of this article was Manuscript.

Available from: 2012-10-15 Created: 2012-10-15 Last updated: 2017-04-10Bibliographically approved

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