advanced diagnostics tools and analysis methodologies in solid oxide fuel cells · 2014-11-17 ·...
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Advanced Diagnostics Tools and AnalysisMethodologies in Solid Oxide Fuel Cells
Mitg
lied
de
r H
elm
holtz-G
em
ein
sch
aft
24. June 2009 J. Malzbender, P. Batfalsky, L. Blum, S. M. Groß, V.A.C. Haanappel, N. H. Menzler, A. Neumann, V. Shemet, R.W. Steinbrech, I.C. Vinke
International Symposium on
Diagnostics Tools for Fuel Cell
Technologies, Trondheim 2009
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24. June 2009 Folie 2
� Role of “Advanced Diagnostics Tools and
Methodologies”
� Post operation methodology
� Post operational analysis methods
� Post operation analysis procedure
� Example G-Design stack
� Improved design
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24. June 2009 Folie 3
Role of “Advanced Diagnostics Tools and Methodologies”
Fabrication
Design
Post Operation
Analyses
Operation
Light weight stack (APU application)
Short stack for SOFC development
F-design
CS-design
Diagnostics Tools / Methodologies
Advanced characterization
methods are an essential
element to understand the stack
performance within the frame-work of a systematic testing
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� Disassembling with selected experts depending on expected degradation
mechanism. Experience in synthesis, production, interaction, thermo-
mechanics, corrosion, thermo-chemistry, sealants, stack / system
operation, single cell testing, microscopy, SEM
� 108 dissections from 8.2002 to 9.2008.
� Electro-chemical results and irregular events are considered.
� A digital photographic image is taken of every stack plane.
� Unusual observations are investigated microscopically during
disassembling.
� After dismantling more detailed SEM (TEM) investigation are carried out.
� Every stack opening is discussed in a subsequent meeting, suggesting
further detailed follow up work.
� Reports are passed on to selected members of the SOFC development
team.
� Selected results are presented to the entire SOFC team in semi-annual
meetings.
Post Operation Methodologie
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24. June 2009 Folie 5
Materialography & Image analysis Macroscopic changes, color
SEM and EDX Microscopic / structural changes,
qualitative chemical analysis,
Wet chemical analysis quantitative, coarse localized
SIMS quantitative, localized
Thermography, computer tomography short circuit localization, porosity
XRD structural changes
TEM local changes, interfaces, reactions
Leakage, liquid dye inspection localization of leakages
Post Operational Analysis Methods
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24. June 2009 Folie 6
Post operation analysis procedure
Example G-Design stack (G1002-04)
Investigation of degradation and failure by comparison of electrochemical
results with stack dismantling results
low power output
G-Design problems :
high degradation rate
0 200 400 600 800 1000 1200 1400
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1
1,2
0,0
0,2
0,4
0,6
0,8
1,0
1,2
Alterung 23.0 ± 0.1%
in 1000 Stunden
über 314 Stunden
Alterung 35.3 ± 0.1%
in 1000 Stundenüber 644 Stunden
Alterung 37.0 ± 0.3%
in 1000 Stunden
über 299 Stunden
Alterung 10.4 ± 0.1%
in 1000 Stunden
über 803 Stunden
Leck in d
er
Da
mpfr
ingle
itung
Spa
nn
ung
/ V
Zeit / h
Stro
md
ichte
/ A/c
m2
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Before further dismantling took place the origin of the short circuiting was
investigated using infrared camera imaging (thermography).
Ceramic glue shows partly red coloring and bubbles.
In addition a short circuiting to the next cassette was detected.
Sealing of cell: ceramic glue
Sealing to next layer: glass-
ceramic
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24. June 2009 Folie 8
D5
Origin of the short circuiting was a deformation
of the manifold.
Mechanically damaged contact layer
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24. June 2009 Folie 9
Cathode side
~ 3,5 - 4 mm
~ 0,2 – 0,3 mm
Small contact width compared to standard design
Stack G1002-3
Standard F2060-1
Air channel
Air channel
Contact
Contact
Air channel
Trace of the contact
width
Origin of low power output
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24. June 2009 Folie 10
Edge of the cell near the sealant
6031.6O
Cr2O31004068.4Cr K
FormComp.
%
Atom
%
Mass
%
Element
Formation of Cr2O3 on the electrolyte
High degradation rate
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24. June 2009 Folie 11
55.621.2O
La2O341.310.735.2La L
CuO3.51.82.8Cu KCoO1.20.690.97Co K
MnO32.819.525.4Mn K
Cr2O321.311.814.5Cr K
FormComp.
%
Atom
%
Mass
%
Element
Modified contact layerEinbettmasse
Einbett
masse
LCC10
New phases
MnOx
Crofer22 APU first
High degradation rate
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24. June 2009 Folie 12
61.323.0O
La2O323.76.220.2La L
ZrO250.917.637.7Zr L
MnO18.911.314.6Mn K
Cr2O36.53.74.5Cr K
FormComp.
%
Atom
%
Mass
%
Element
Chromia composites near the three
phase boundary
High degradation rate
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Problem:
� Short circuit due to local upwards bending
of the manifold (creep effect)
� Cr2O3 reaction products (from gas phase)
were detected on the surface of the
electrolyte
� New reaction products were detected in
the contact layer (influence of the ceramic
glue)
� Chromia composites were found near the
three-phase boundary which might be
associated with the high degradation
Solution:
� Application glass-ceramic support
point
� Substitution of ceramic glue by glass
– ceramic sealant
� Components of the ceramic glue
could be confirmed, a follow up stack in
the same design with glass – ceramic
sealant had a degradation of (2,6-2,8)%
/ 1000h compared to (23-35%).
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24. June 2009 Folie 14
Cracks in cell, green color suggests re-oxidation
Application point of glass-ceramic support point
Manifold bend
towards anode side Manifold bend
towards anode sideApplication point of glass-
ceramic support point
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24. June 2009 Folie 15
Cut
Air inlet Air outlet
Large manifold made from thin metal
sheets is not geometrically stable at
high temperatures
Results are short circuit or cell
fracture
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Improved Design
Using a combination of
metallic and glass-ceramic
sealants.
Significantly reduced size of
unsupported manifold.
In addition asymmetric cell
to permit smaller in-plane
gradient on thermal cycling.
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24. June 2009 Folie 17
Stack-Dismantling
Jürgen Malzbender
Vincent Haanappel
Norbert Menzler
Peter Batfalsky
Rolf Steinbrech
Ico Vinke
Thank you for your attention