Technical Communication

Easy sintering of silver doped lanthanum strontium

manganite current collector for solid oxide fuel cells
Chuan Wang, Xianshuang Xin, Yanjie Xu, Jianyin Chen, Le Shao, Juan Zhou,
Shaorong Wang*, Tinglian Wen
CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences (SICCAS),
1295 Dingxi Road, Shanghai 200050, PR China
a r t i c l e i n f o
Article history:
Received 4 March 2011
Accepted 20 March 2011
Available online 16 April 2011
Keywords:
Solid oxide fuel cell
Current collector
Contact resistance
Silver doped lanthanum strontium
manganite
a b s t r a c t
A new system, (La
0.8
Sr
0.2
)
1x
Ag
x
MnO
3d
(LSAM, x 0.2), is developed as current collector for
solid oxide fuel cell (SOFC). LSAM is prepared by a modied solegel method and presents
a single phase. The shrinkage temperature reduces from 1150

C to 800

C with an addition
of 15 mol% Ag to La
0.8
Sr
0.2
MnO
3d
(LSM20). The contact resistance between the current
collector and the cathode is measured, and the inuence of Ag content on the contact
resistance is investigated. The result shows that the contact resistance using
(La
0.8
Sr
0.2
)
0.85
Ag
0.15
MnO
3d
(LSAM15) as current collector is about 12 mU cm
2
at 750

C,
which is close to the value using expensive Pt paste as current collector. This new system is
a promising current collecting material for the practical application of SOFC.
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
Solidoxidefuel cells(SOFCs) aredeviceswhichconvert chemical
energy into electricity directly without combustion as an inter-
mediate step. SOFC gives much higher conversion efciency
thanconventional energy systems [1e3]. However, an SOFChas
the open circuit voltage of only about 1 V. Therefore, to achieve
higher voltages, a number of cells are usually electrically con-
nected in series in a stack via interconnectors which separate
the fuel onthe anode side of one cell fromthe air onthe cathode
side of the adjacent cell [4,5]. The reason for using a metallic
material rather than a LaCrO
3
-based ceramic material as an
interconnector is because the former has the advantages of
higher electronic and heat conductivity, excellent ductility,
lower cost and so on [6,7]. However, the contact resistance
induced by the weak contact or the resistive interfacial scale
formation between metallic interconnectors and ceramic elec-
trodes cannot be ignored [8,9]. This problem can be solved by
adding a current collecting layer between the interconnector
and the electrode for better electrical contact [10]. Such current
collecting layer has no direct role in electrochemical reaction,
but it canprovideahomogeneouscontact over the wholeareaof
the fuel cell and minimize the ohmic losses within the stack.
Nickel metal paste and nickel mesh are typically utilized as
current collector on the anode side to reduce the resistance
betweenthe nickel-basedanode anda metallic interconnect. As
a result, contact resistance loss of the anode side is relatively
small. However, it is more challenging toachieve low-resistance
* Corresponding author. Tel./fax: 86 21 52411520.
E-mail address: srwang@mail.sic.ac.cn (S. Wang).
Avai l abl e at www. sci encedi r ect . com
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i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 7 6 8 3 e7 6 8 7
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.03.127
contact on the cathode side, where at least one ceramicemetal
interface and possibly several ceramiceceramic interfaces are
present.
Either noble metals or conductive ceramics can serve as the
current collector. Noble metals suchas platinum, silver and gold
present a cost disadvantage. At the same time, because of the
mismatch of thermal expansion coefcient (TEC) between the
current collector layer and cathode [11], the state of attachment
and then the contact resistance may be changed during thermal
cycling of a stack. One way to solve this problem is adding an
unsintered ceramic layer (green paste or sheet) on the cathode
surface before assembling the single cell, and the green sheet is
soft and can change its local shape to t the space between the
interconnector andcathode, sothat thecontact will beimproved.
It is preferred that the unsintered soften ceramic layer can then
be sinteredat temperatures corresponding to that at whichglass
seals are typically formed(850e1050

C) [12,13]. It is because that

the alloy interconnector cannot withstandahightemperature in
air. Then a lower sintering temperature of the current collecting
layer is required. A well-sintered ceramic layer will have good
grain boundary which helps to improve the conductivity and to
provide sufcient electrons to the cathode for the reduction of
oxygen. Lanthanumstrontiummanganite(LSM) generallymeets
therequirement of thecurrent collectingpastematerial, withthe
exception of a higher sintering temperature. Megel et al. [14]
reported that partial substitution of cobalt for manganese could
lower the sintering temperature of LSM. McCarthy et al. [15]
demonstrated that sintering of (La
0.9
Sr
0.10
)
0.98
MnO
3d
(LSM10)
occurred substantially faster when being exposed to alternating
exposure of air and nitrogen (10 ppm O
2
) than in air for temper-
ature of about 1000

C. In this paper, silver doped lanthanum
strontium manganite, (La
0.8
Sr
0.2
)
1x
Ag
x
MnO
3d
(LSAM), is devel-
oped. The effects of silver content on the phase structural,
thermal expansion behavior, sintering shrinkage rate and elec-
trical properties of LSAM are reported.
2. Experimental
2.1. Synthesis of LSAM powder
(La
0.8
Sr
0.2
)
1x
Ag
x
MnO
3d
samples with x 0(LSM20),
0.05(LSAM5), 0.10(LSAM10), 0.15(LSAM15), 0.20(LSAM20) and
0.30(LSAM30) were prepared using a modied solegel method
[16]. Analytical grade La
2
O
3
, SrCO
3
, AgNO
3
and MnCO
3
were
used as starting materials. Starting materials were rstly dis-
solved using nitric acid or water. The solution of metal nitrates
was mixed with a citric acid aqueous solution, with the molar
ratio of total metal cations to citric acid being set at 1:2.
Ammonia was added to adjust pH to 7, and then water was
evaporateduntil agel was obtained. Thegel was driedat 120

C.
And then were calcined at 800

C for 3 h. A Rigaku X-ray
diffractometer (D/Max 2500/K, Japan) was used to record
diffract patterns with a range of 10e80

, a step of 0.01

and
a scan speed of 2

min
1
.
2.2. Evaluation of the samples
For sintering behavior, electrical conductivity and TECstudies,
cylindrical compact samples of the ceramic powders were
prepared by uniaxial pressing at a pressure of 150 MPa. The
length and diameter of the compacted samples were about
15e20 mmand5e6 mm, respectively. Sintering behavior of the
samples was studiedusing a NETZSCHDIL 402Cdilatometer in
air at a heating rate of 5

C min
1
. The cylindrical specimens
were heated to 1000

C at 2

C min
1
in air and held at this
temperaturefor 2htomeasureapparent conductivityandTEC.
The apparent densities of all the samples were estimated by
the dimensions and the weight of the samples. The relative
density was expressed as a percentage of the apparent density
to the theoretical density. TEC measurements were conducted
using a NETZSCH DIL 402C dilatometer in air with a heating
rate of 5

C min
1
. After that, electrical conductivity was
measured via the four-probe DC method.
2.3. Contact resistance measurements
A-site decient LSM was previously reported to exhibit high
sintering activityinair andnitrogencomparedtoordinaryLSM
[17]. (La
0.8
Sr
0.2
)
0.9
MnO
3
(LSM90) powder was synthesized by
a solid state reaction method. The LSM90 powder was used to
prepare a LSM90 lm of w150 mm in thickness with a tape
casting method. The LSAM current collector was screen
Fig. 1 e Schematic drawing to test the contact resistance.
Fig. 2 e X-ray diffractograms of the LSAM for x [ 0e0.3.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 7 6 8 3 e7 6 8 7 7684
printed onto the both sides of the sintered LSM90 lm(relative
density 95%). ThenCrofer 22 APUwas attached to bothsides of
LSAMcurrent collector tomeasurethecontact resistance. Fig. 1
shows a schematic drawing of the contact resistance test. The
measurement was carried out from 850

C to 600

C in air by
a four-probe DC method. The samples were red in air from
room temperature to 850

C and held for 1 h, and then started
measuring area specic resistance from850

Cto 600

C. It was
kept half an hour at each test temperature point. To evaluate
the experimental result, Pt paste was also brushed onto the
LSM lm and tested as a reference.
3. Results and discussion
The X-ray diffraction patterns of the (La
0.8
Sr
0.2
)
1x
Ag
x
MnO
3d
(x 0e0.3) are shown in Fig. 2. The diffractograms are similar
to that of the La
0.8
Sr
0.2
MnO
3d
(LSM20) [18]. The XRDpattern of
the sample with x 0.2 exhibits additional diffraction peaks,
which are marked by triangle. The impurity is identied as
silver phase (Ag), and it is formed probably due to the metal
ions properties relative to other cations, such as a large ionic
radius, a high polarizability, a lowacidity and a tendency to be
free in the metal citrate environment [19,20]. LSM20 is
a perovskite structure, and there is two main perovskite peaks
in the 2q region, 32e33

. The partial substitution of La (Sr) by

Ag results in signicant variations of the hexagonal unit cell
parameters (a and c) which can be seen in Table 1. The more
sites the Ag ions occupy, the more Mn
3
ions are oxidized to
Mn
4
. The lattice constant a decreases when increasing the Ag
content, as indicated in Table 1. This is because that Mn
4
radii is smaller than Mn
3
radii (r
Mn3
0.064 nm,
r
Mn4
0.053 nm) [21] and the MneObond length decreases as
a consequence of the increasing amount of Mn
4
. The change
of lattice constants also accounts for that Ag ions really
occupy A-site in the perovskite structure.
Relative density, open porosity, TEC, and electrical
conductivity of LSAMare also shown in the Table 1. In order to
make the data valuable for stack preparation, the sintering
temperature of samples is adopted at 1000

C in present work,
wherea greencurrent collecting layer will be usedandsintered
at the sealing temperature of 1000

C. The relative densities
increase and open porosity decrease with increasing Ag addi-
tions. Most of the pores are open pores so that the oxygen can
diffuse trough the current collector layer easily. The TEC value
between 30

C and 900

C increases with the increasing Ag
content for LSAM, ranging from 12.04 10
6
K
1
to
13.67 10
6
K
1
. One reason may be due to the increasing
relative density of the sample with increasing Ag content. For
x 0.3, there is a Ag phase existing. The TECof pure Ag is much
bigger thanthat of LSM, resulting inlarger TECvalue. Electrical
conductivity of the LSAMincreases greatly with the increasing
of Ag content due to the pronounced increase in relative
density of samples and the increase of carrier concentration
when Mn
3
is oxidized into Mn
4
.
Fig. 3 presents the dilatometric curves of LSAM (x 0e0.3).
The shrinkage temperature decreases from1150 to 800

Cwith
the doping of 15 mol% Ag to LSM20, indicating that doping Ag
to A-site of LSM helps to improve the sintering activity. Tai
et al. reported that the Co doing would reduce the activation
energy of the system La
0.8
Sr
0.2
Co
1y
Fe
y
O
3
[22]. Such case may
also occur in LSM system. The relative shrinkage increases
with Ag doping amount owing to the improvement of sinter-
ing activity. For the case of x 0.15e0.3, the shrinkage
decreases again, however, the relative density keeps large
(Table 1). This may be due to the larger green density of the
sample for x 0.2 and 0.3.
Fig. 4 shows the relationship of contact resistance versus
temperature. Adding a current collecting layer onto the LSM
lm can decrease the contact resistance obviously. The
contact resistance decreases with the increase of Ag content,
which is coincidence with the result of conductivity experi-
ment. The contact resistance of LSM20 is too high because it
Table 1 e Lattice constants (a and c), relative density, open porosity, TEC, and electrical conductivity of the LSAM with
x [0e0.3.
Parameters LSAM with x
0.00 0.05 0.1 0.15 0.20 0.30
a (A

) 5.52897 5.52792 5.52665 5.52458 5.52365 5.52226

c (A

) 13.3679 13.3689 13.3701 13.3726 13.3766 13.3776

Relative density (%) 48.76 63.37 65.24 77.21 78.25 83.06
Open porosity (%) 48.93 35.62 30.26 20.36 18.28 15.57
TEC (10
6
K
1
) 12.04 12.26 12.51 12.67 12.89 13.67
Electrical conductivity (S cm
1
) 33.41 54.62 87.35 126.36 200.45 270.57
Fig. 3 e Dilatometric curves of LSAM for x [ 0e0.3
measured at a heating rate of 5

C min
L1
in air.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 7 6 8 3 e7 6 8 7 7685
cannot be sintered well at 1000

C. The contact resistance of
LSAM15 is about 12 mU cm
2
, which is almost the same as Pt
paste. As is given in Fig. 5, the contact resistance of an inter-
connector/current collector/cathode sandwich specimen
evaluated as a function of time at 750

C. The resistance is
initially about 12 mU cm
2
, and it is stable throughout the test
time of 110 h. The results show that the new LSAM current
collecting layer has the potential to greatly improve the
contact between an LSM cathode and an alloy interconnector.
4. Conclusion
Anewsystem, single phase (La
0.8
Sr
0.2
)
1x
Ag
x
MnO
3d
(LSAM), is
developedas current collector for solidoxide fuel cells (SOFCs),
which can be obtained when x is less than 0.2 by a modied
solegel method. Results indicate that silver doping in
lanthanum strontium manganite can effectively lower the
sintering temperature. As a result, the contact resistance
betweenthecathodeandthecurrent collecting layer decreases
withthe increasing of Ag content, and the contact resistance is
almost the same as Pt paste as current collector when the x is
0.15. Therefore, the new perovskite-type system
(La
0.8
Sr
0.2
)
1x
Ag
x
MnO
3d
(x 0e0.15) is a promising current
collectingmaterial for solidoxidefuel cells. Duringtheworking
state, the Ag

may be oxidation from the lattice site, and then

migrate to the interface between cathode and current collec-
tion layer, and the performance of cell would be worsen.
Acknowledgments
The authors are grateful for the nancial support from the
Science and Technology Commission of Shanghai Munici-
pality (No. 08DZ2210900), the Chinese Government High Tech
Developing Project (2007AA05Z151) and the National Natural
Science Foundation of China (51071169).
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