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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
A R T I C L E I N F O
Article history:
Received 22 August 2016
Received in revised form 4 December 2016
Accepted 5 December 2016
Available online 5 December 2016
Keywords:
Solid Oxide Fuel Cell
stack
contact problems
cathode contact
thermal expansion coefcient
performance
A B S T R A C T
The successful operation of solid oxide fuel cells (SOFC) imposes high demands on the similarity of the
thermal expansion coefcients of the materials used. This is not only due to thermo-mechanical factors
but also because of the risk of contact loss via the formation of a micro-gap between the electrodes and
adjacent contact layers caused by temperature changes. The origin of the formation of such a gap
between the different layers in an SOFC stack is investigated on the basis of various material
combinations. A comparison with successful and failed stack test results reveals that there is a high
probability of contact problems if the calculated gap on the cathode side exceeds 200 nm. This limit
relates to the maximum possible elastic deformation of the combination of the cathode and cathode
contact layer (CCL). Such contact problems can be avoided in the current design by utilizing an
appropriate combination of the cathode, CCL and glass-ceramic material that can be selected on the basis
of the methodology outlined in the current work. This optimization in materials selection will help to
establish a stack technology that allows high power density with a minimized risk of failure of single
layers.
2016 Elsevier Ltd. All rights reserved.
1. Introduction
High temperature fuel cell stacks must meet the critical
requirement that all layers (all parts of a single plane or repeating
unit, like anode, electrolyte, cathode, contact layers, protective
coating, interconnect) have to retain good electrical contact,
although large temperature changes occur between sealing
temperatures (in this case, using a rigid glass sealing) or assembly
temperatures (e.g., in the case of using a mica sealing) and
operating temperatures (which can span a relatively wide range).
In an ideal case, all materials would have the same thermal
expansion coefcient (TEC) and no problem would arise. But in real
congurations, differences will emerge that can cause thermomechanical stress, which is investigated in numerous publications
[19]. A further problem can occur because of the differences in the
TECs of the different materials which result to a different change in
thickness of the various layers. While changing temperature from
the starting point (which can be the sealing or assembly
temperature, depending on the sealing concept used) to the
operating point, this different changes in thickness can lead to
contact loss at the mechanically weakest point which, in most
* Corresponding author. Tel.: +49 2461 61 6709, fax: +49 2461 61 6695.
E-mail address: l.blum@fz-juelich.de (L. Blum).
http://dx.doi.org/10.1016/j.electacta.2016.12.016
0013-4686/ 2016 Elsevier Ltd. All rights reserved.
Nomenclature
ASC
BSCF
CCL
CGO
LC
LCC
LCC10/12
LSCF
LSM
MMA
NCO
SOFC
TEC
YSZ
atec
dL0
d(T)
dc
Ddel
DdL
Ddr
E
e
emax
s
s max
T
Tmax
density is increased and the stack becomes hotter. From Fig. 1 it can
also be seen that the problem is quite complex, because not all
layers show the same behavior. This is affected by various
properties like variations in materials, the local temperature and
mechanical strength of the interfaces and the local dimensions
inuenced by manufacturing tolerances.
In the present work, as a rst approach the bathtub behavior is
analyzed concentrating on the differences in the thermal
101
Fig. 1. Current-voltage characteristics of 5-plane stack F2005-05 and 10-plane stack F2010-06, with several planes showing bathtub behavior.
102
Fig. 2. Simplied assembly sketch of F-design stacks with a thickness of dL0 of the layers at Tmax.
Fig. 3. Thermal expansion coefcient of components relevant for the cathode side and of Crofer 22 APU for reference [1424].
103
Fig. 4. Thermal expansion coefcient of components relevant for the anode side [14,15,24,25].
atec
dT d25 C
=T 25 C
d25 C
with T temperature in C
d(T) thickness of the layer at temperature T
d(25 C) thickness of the layer at 25 C
The following assumptions have been made:
Table 1
Calculation sheet to obtain the value of the gap: here as example for the gap between the cathode and cathode contact layer (CCL).
[1]
Thickness of
layer b):
[2]
T
atec
mm
between
25 C and T
106 K1
200
900
860
800
750
700
650
600
500
400
300
200
25
12.33
12.22
12.11
12.03
11.96
11.90
11.85
11.76
11.73
11.60
10.99
[3]
Change of thickness of layer b)
between T and 25 C
[4]
Reduction of thickness of layer b)
compared to Tmax
[5] [6]
! Change of the thickness of a)
compared to Tmax
mm
mm
mm
[7]
a) b) >0 ! gap
cathode
- CCL
mm
2.157
2.041
1.877
1.745
1.615
1.487
1.361
1.118
0.880
0.638
0.385
0
0.000
0.116
0.280
0.412
0.542
0.670
0.796
1.039
1.277
1.519
1.772
2.157
0.000
0.124
0.296
0.432
0.566
0.700
0.837
1.116
1.399
1.669
1.909
2.203
0.000
0.008
0.016
0.019
0.023
0.030
0.041
0.077
0.122
0.150
0.137
0.046
104
Fig. 5. Formation of gap on the cathode side in the case of different glass-ceramic types and sealing temperatures using an LSM cathode and LCC10 as the contact layer: a) total
temperature range; b) in a 600-900 C temperature range.
105
because the mechanical strength was not sufcient, another glassceramic type was developed: glass-ceramic H with the addition of
20%YSZ bers. If this glass-ceramic is sealed for 10 hours at 850 C,
a relatively high amount of amorphous glass phase remains. This
can be seen in the curvature of the thermal expansion coefcient of
between 600 and 700 C. In the operating temperature range, the
resulting gap is relatively small but increases down to room
temperature and becomes similar to glass-ceramic G (see Fig. 5a).
However, because of the high amorphous content, the mechanical
properties are still not good enough and, in addition the glassceramic changes its behavior during operation by increasing the
content of its crystal phase which changes the thermal expansion
behavior again. To improve both, the sealing time at 850 C was
increased to 100 hours, resulting in higher mechanical strength
[26]. However, the thermal expansion coefcient goes down,
resulting in a somewhat bigger gap. Another very promising glassceramic material development was glass-ceramic B, which has a
sealing temperature of 950 C and a much better adapted thermal
expansion coefcient, resulting in the smallest gap size. However,
the experiments revealed that this glass-ceramic has too high a
viscosity during the sealing process, so it cannot be used to seal the
cell. Therefore, it was combined with glass-ceramic H, which
resulted in good thermomechanical stability and gastight stacks
[13]. However, the processing of glass-ceramic H at 950 C results
in a much larger gap, especially in the operating temperature range
(see Fig. 5b).
Fig. 6. Formation of the gap on the cathode side in the case of different glass-ceramic types and sealing temperatures using an LSCF cathode in a 600-900 C temperature
range: a) with LCC10 as the contact layer, b) with LCC12 as the contact layer.
106
Fig. 7. Formation of a gap on the anode side in the case of different glass-ceramic types and sealing temperatures.
Ddel dc e dc
s
E
where dc is the thickness of the CCL plus cathode, which in our case
is 200 mm (see Fig. 2).
The compression stress s can be calculated based on the
compression force during the sealing process, while the glassceramic sealing is still soft and the contact area on the cathode side,
which is based on the channel structure, makes up about 40% of the
107
Table 2
Mechanical properties of porous ceramic layers and resulting deformation during sealing, taking the E-modulus at RT and at 800 C.
Material
BSCF
Porosity
Sintering
E-Modulusa
ERT E800
Fracture Strengthb
GPa
MPa
800 C
RT
800 C
24
31
34
50
1200 C/3h
1000 C/10h
35
33
LSCF
46%
1200 C/5h
12
MMA
24,5%
1500 C
70
LCC
LC
dense
dense
CGO
43%
a
b
18
54
30
Lit.
RT
34%
38%
1050 C/4h
s max,RT s max,800
26
F20
nm
F10
nm
F20
nm
800 C
RT
[28]
[27]
1.8
1.9
2.6
2.7
[28]
5.1
7.5
[29]
0.9
1.3
141
76
140
70
[30]
[30]
0.4
0.8
0,6
1.2
57
55
[28]
1.1
1.6
2.6
3.8
1.1
1.7
Mean values.
Loading rate 100 N/min (T-change within 30 to 60 min).
cathode area. The resulting values for the F10 and F20 designs are
outlined in Table 3.
Based on these values, the possible elastic deformation during
sealing is calculated. The results are given in Table 2. The maximum
deformation result was 7.5 nm for porous LSCF with mechanical
properties for 25 C. Assuming the same temperature dependency
as reported for BSCF [28], the resulting deformation at 800 C
would be 10.4 nm. This value is at least one order of magnitude
below the deformation of the ceramic layers needed to avoid gap
formation due to the differences in thermal expansion while
relaxing compression during cooling to operating temperature.
This means the connection between CCL and the cathode
(respectively the layers themselves) will be subject to tensile
stress during this cooling process. The deformation until rupture
Ddr can be calculated by
Ddr dc emax dc
s max
emax
Dd_r
(related to
200 mm)
%
Table 3
Compression stress s during the sealing process in case of design F10 and F20.
Loading
Stress s
Area
F10
N
F20
N
F10
mm2
F20
mm2
F10
MPa
F20
MPa
1000
6500
3240
14440
0.309
0.450
RT
BSCF
LSCF
MMA
LCC
LC
CGO
0.089
0.103
0.150
0.043
0.099
0.092
0.096
nm
800 C
0.210
0.048
RT
177
206
300
86
199
184
193
800 C
421
96
108