Solid State Ionics 177 (2007) 3455 3460

www.elsevier.com/locate/ssi

Fabrication and performance of anode-supported

YSZ films by slurry spin coating
Kongfa Chen a , Zhe L a,, Na Ai a , Xiqiang Huang a , Yaohui Zhang a , Xiaodong Ge a ,
Xianshuang Xin a , Xiangjun Chen b , Wenhui Su a,c,d
a
Center for Condensed Matter Science and Technology, Harbin Institute of Technology, West Dazhi Street 92#, Harbin, 150001 China
b
Division for Theoretical Physics, Harbin Institute of Technology, Harbin, 150001 China
c
Department of Condensed Matter, Jilin University, Changchun 130022 China
d
International Center for Material Physics, Academia, Shenyang 110015 China
Received 3 April 2006; received in revised form 11 August 2006; accepted 2 October 2006

Abstract

Yttria-stabilized zirconia (YSZ) thin films were fabricated by slurry spin coating on NiO-YSZ anode substrates. The effect of processing
factors, such as the baking temperature and spinning number was investigated and discussed. According to the thermogravimetric analysis, the
organic additives could be removed by baking at 400 C for 10 min. Under this heating condition for each coating, the defects in the electrolyte
film could be repaired by repetitive coating. Dense and crack-free electrolyte films were consequently obtained. When dry hydrogen was used as
the fuel and the stationary air as the oxidant, a single cell based on a 14-m-thick YSZ film produced open-circuit voltages (OCVs) of N1.10 V in
all of the operating temperatures (500700 C). The cell exhibited maximum power densities of 634, 493 and 316 mW/cm2 at 700, 650 and
600 C, respectively. By using pure oxygen at a flow rate of 100 mL/min, the maximum power density increased to 658 mW/cm2 at 650 C.
2006 Elsevier B.V. All rights reserved.

Keywords: Solid oxide fuel cells (SOFCs); Slurry spin coating; Baking temperature; Spinning number; Defect; Electrolyte thin film

1. Introduction manufacturing of thin electrolyte films and is less restricted by the

geometric factors. This includes tape casting [2], slurry coating
Solid oxide fuel cells, SOFCs, have a great potential to be [46], spin coating [79], dip coating [10], etc.
the cleanest, most efficient, and versatile technologies for the In the case of slurry coating, to form a suitable slurry com-
chemical-to-electrical energy conversion [1]. Up to now, yttria- position, many organic additives are required to be propor-
stabilized zirconia (YSZ) is a commonly used electrolyte material tionally added and ball-milled together with the electrolyte
due to its pure ion conductivity, good chemical compatibility and powders. Moreover, in order to avoid cracks during removal of
excellent mechanical properties [2]. However, the conductivity of the organic additives, very careful drying and/or baking and
YSZ is not sufficiently high to reduce the ohmic loss for SOFCs sintering processes have to be adopted, which usually needs to
operating in intermediate temperatures (600800 C), it is thus be repeated several times. As a result, the whole process is
desirable to fabricate electrolyte films with only a few microns complex and time-consuming. As far as the spin coating method
thick. is concerned, various compositions of YSZ precursor liquids
Nowadays, special attention has been paid to the development have been employed, such as YSZ polymeric sol [7,8] and YSZ-
of anode-supported electrolyte thin films SOFCs [3]. Colloidal- ethanol suspension [9]. Currently, the electrolyte thickness
based process is a simple and cost-effective method for the employed is about 10 m, and further reductions in electrolyte
thickness are likely to lead to reliability problems with
Corresponding author. Tel.: +86 451 86418420; fax: +86 451 86412828. electrolyte integrity [11]. Also, the deposition rate of the spin
E-mail address: lvzhe@hit.edu.cn (Z. L). coating techniques reported in the literature seems relatively
0167-2738/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2006.10.003
3456 K. Chen et al. / Solid State Ionics 177 (2007) 34553460

low to fabricate electrolyte films with this thickness. For deposited on the sintered YSZ films. Followed by sintering at
example, a 10-m-thick dense YSZ film was obtained after 1100 C for 2 h, the cathodes were then impregnated by a
repeating the coating-drying cycle for 20 times [9]. In addition, Sm0.2Ce0.8(NO3)x solution, and calcined at 850 C for 1 h. The
Kim et al. [7] prepared a 1.9-m-thick YSZ film on the impregnationcalcination cycle was repeated for three times.
Ce0.8Y0.2O1.9 (YDC) substrate via 6 coating-heating cycles. Thermal gravimetric analysis (TGA) of the decomposition of
Slurry spin coating method [12] is a combination of slurry ethyl cellulose was performed with a thermal analyzer (SDT
coating and spin coating techniques. A homogeneous and stable 2960, TA Instruments, USA) from room temperature to 600 C.
YSZ slurry is employed by simply mixing YSZ powders with The heating rate was 5 C/min and the air purge flowing rate
organic additives consisting of ethyl cellulose and terpineol was 100 mL/min. Mass changes of a newly coated single-
together, instead of the conventional polymeric YSZ sol or layered YSZ film versus baking temperature were also per-
YSZ-ethanol suspension. Without the process of drying in air, formed by weighing the sample immediately after baking at
the as-prepared green YSZ films require no strict heating and some temperature points, using an electronic balance (BP211D,
cooling rates during processing, and therefore the procedure Sartorius, Germany).
becomes efficient and fast. Furthermore, the deposition rate Fuel cells were tested with a four-probe method. Concerning
is high due to the relatively high YSZ content in the slurry, e.g., a single cell, a silver paste (DAD-87, Shanghai Research
9-m-thick electrolyte film was fabricated by three coatings Institute of Synthetic Resin, China) was applied on the anode
[13]. and cathode as the current collector, followed by attaching two
In this paper, fuel cells based on YSZ thin films were silver wires to each electrode as current and voltage leads,
fabricated by this technique. A single cell with a 14-m-thick respectively. Then the cell was sealed on one end of an alumina
YSZ film produced maximum power densities of 493 and tube with the silver paste. Dry hydrogen was used as the fuel at
316 mW/cm2 at 650 and 600 C, respectively. The effect of the the anode side, and the stationary air as the oxidant at the
baking temperature and spinning number on the microstructure cathode side. For the purpose of comparison, pure oxygen flow
and performance of electrolyte thin films was studied and was also introduced at the cathode in some cases. Electrochem-
discussed. Electrochemical characteristics of the single cell ical characteristics were performed with SI 1287 and SI 1260
were also conducted and presented in this study. (Solartron Instruments, Hampshire, UK). As for the impedance
spectra measurement, the frequency range was from 0.1 Hz to
2. Experimental 91 kHz. The operating temperature was varied from 500 to
800 C. Morphologies of the cells after electrochemical testing
NiO powders were synthesized by the precipitation method were characterized by a scanning electron microscope (SEM, S-
[12], using Ni(NO3)26H2O (analytical reagent, A.R.) and 570, Hitachi, Japan).
ammonia (A.R.) as the raw materials. The resultant powders
were calcined at 4001000 C for 2 h. NiO, YSZ (TZ-8Y, Tosoh 3. Results and discussion
Corp.) and flour were mixed in a weight ratio of 5:5:2, and ball-
milled with ethanol media. After drying, the green powders 3.1. Effect of the baking temperature and spinning number
were uniaxially pressed into pellets at 200 MPa with a dia-
meter of 13 mm, which were subsequently calcined at 1000 C During the course of studying the slurry spin coating tech-
for 2 h. The anode substrate was 0.60.7 mm thick. nique, we found certain key processing factors, i.e., the baking
YSZ (TZ-8Y, Tosoh Corp.) powders were mixed with ethyl temperature and spinning number had significant effect on the
cellulose (chemical reagent, residue on ignition 0.2 wt.%, microstructure of the electrolyte films. Therefore, the present
chloride 0.08 wt.%, Fe 0.005 wt.%) and terpineol (A.R.) in study was mainly concentrated on these two important factors.
a weight ratio of 25:3.4:71.6 in a mortar and pestle to form a Fig. 1 shows the open-circuit voltages (OCVs) of the cells
homogeneous and stable electrolyte slurry, which had a vis- measured at 800 C in the two batches. Each layer of the as-
cosity of 35 Pa s. The slurry was then spin coated on the anode
substrates at 6000 rpm for 60 s using a spin coater (KW-4A type,
Chinese Academy of Sciences). In order to study the effect of
baking temperature, two batch samples were prepared. In the
first batch, each layer of the as-prepared green film was baked
at 80 C for 20 min before depositing the next layer. In the
second batch, each of the YSZ layer was baked at 400 C for
10 min with an average heating rate of 2070 C/min and a
cooling rate of 4070 C/min. Finally, the bilayers were co-
sintered at 1400 C for 4 h.
Sm0.2Ce0.8O1.9 (SDC)-impregnated La0.7Sr0.3MnO3 (LSM)
cathodes [13] were adopted. LSM powders were synthesized by
the Pechini method, and the precursor powders were subse-
quently calcined at 1000 C for 2 h. LSM and activated carbon
mixture was mixed with terpineol and ethyl cellulose, and Fig. 1. OCVs of the cells in the two batches measured at 800 C.
 K. Chen et al. / Solid State Ionics 177 (2007) 34553460 3457

Fig. 2. Microstructures of the cells: a) a single-layered film and b) a three-layered film in the first batch; c) surface of a three-layered film and d) cross-section of a single
cell based on the three-layered electrolyte film in the second batch.

prepared green YSZ film in the first and in the second batches additional layer. Whereas, a balance should be achieved be-
was baked at 80 and 400 C during the processing procedure, tween a reasonable electrolyte thickness and cell gas-tightness,
respectively. As for the first batch, the single- to four-layered in order to minimize the electrolyte ohmic resistance and en-
film cells produce OCVs of 0.61, 0.70, 0.86 and 0.77 V, hance the cell performance. As a consequence, a three-layered
respectively. It can be seen that cell OCVs in this batch are all YSZ thin film with each layer baked at 400 C for 10 min is
less than 1.0 V, indicating a large amount of gas permeation suitable in the following studies.
through the cell due to insufficiently gas-tight electrolyte films. Shown in Fig. 2 are the micrographs of the cells in the two
The OCVs ascend slowly with the increase of the spinning batches. Fig. 2a,b shows the surfaces of a single-layered and a
number, and even descend when the coating number reaches three-layered YSZ films in the first batch, respectively. Fig. 2c,d
four. By repetitive coating, defects of the films could be repaired shows the surface of a three-layered YSZ film in the second
as reported in the literatures [8,10]. This is partly supported by batch and the cross-section of a cell based on the three-layered
the fact that OCVs of the multi-layered film cells in the first film and SDC-impregnated LSM cathodes after electrochemical
batch are all higher than that of the single-layered film cell. testing. In the first batch, as a whole, the YSZ grains contact
In the literatures [2,7,14], very careful drying and baking well with each other (see Fig. 2a). However, there are still some
procedures were applied, in order to avoid the formation of small defects existing, such as small pores and pinholes, which
defects during evaporation or burnout of the various organic could lead to the leakage of the gases through the electrolyte and
additives. In the present study, the organic additives in the green thus lower the OCV. In the case of the three-layered YSZ film,
YSZ film was removed by heat-treated at 400 C for 10 min there is a big open pore in the center besides some non-
before the coating of additional YSZ layer. The improved result homogeneous smaller defects (Fig. 2b). However, OCV of the
in the second batch is also shown in Fig. 1. As for the second three-layered film cell is still 0.25 V higher than that of the
batch, the two- to four-layered film cells yield OCVs of 1.05, single-layered film cell. It is probable that the scale of the big
1.14, 1.14 V, respectively. The more the spinning number, the pore is not deep enough to reach the anode substrate, and the
higher the OCV. Other than the single-layered film cell, all of defects in the underneath layers should have been repaired to
them exhibit OCVs of N 1.0 V, indicating that the films are gas- some extent. In the second batch, according to the surface
tight and pinhole-free. This result demonstrates that by adopting image, the grains contact well with each other, and no cracks or
reasonable processing parameters, the defects in the former pinholes can be found within the view (Fig. 2c). As can be
layer could be successfully repaired by the deposition of observed in Fig. 2d, the Ni-YSZ anode shows a porous
3458 K. Chen et al. / Solid State Ionics 177 (2007) 34553460

Fig. 3. a) TGA of the decomposition of ethyl cellulose and b) mass loss of a

newly coated single-layered YSZ film versus some temperature points.
Fig. 4. IV and IP characteristics of the cell with the cathode exposed to the
stationary air.
microstructure, and the pores are not so uniformly distributed.
The YSZ layer is well adhered to the porous anode substrate,
and appears to be dense, uniform and without cracks and consequence, only a small proportion of terpineol and all of ethyl
pores. The film is 14-m-thick, with an average thickness of cellulose are left inside the electrolyte film after baking at 80 C
4.7 m for each coating. The cathode layer is 16 m-thick, for 20 min.
has some big pores in it and seems somewhat dense, indicating Although the single-layered film was baked at 80 C, it
the formation of a continuous and porous network of SDC phase actually has experienced the heat-treating course at 400 C
within the LSM structure [15]. during co-sintering procedure. Therefore, there is no difference
The major disadvantage of the colloidal process is the strain in the microstructure for a single-layered film under different
induced during drying or heating, which may result in some baking conditions. Based on the surface morphology in Fig. 2a,
processing defects [8]. However, this seems not to be the case in it could be concluded that for a single-layered green film, the
this study, as no distinct cracks could be seen in Fig. 2a. There organics could be easily removed through the film surface,
should be some thing to do with the organic additives. Fig. 3 leaving some small defects. While for a three-layered green film
shows the TGA of the decomposition of ethyl cellulose and mass in the first batch, some of the organics are still accumulated
changes of a newly coated single-layered YSZ green film as a inside each coating after baking at 80 C. During sintering, the
function of baking temperature, i.e., room temperature (25 C), organics within the top layer are easy to burn out just like the
80 C for 20 min, 150 and 180 C for 10 min, respectively. With case in the single-layered film. However, the organics trapped
respect to the TGA result, ethyl cellulose typically loses inside the films would decompose at high temperatures and the
absorbed water initially, then decomposes between 180 and decomposition and gas evolution would expand and push the
420 C. At 400 C there is only 9.78 wt.% of the original mass YSZ electrolyte film, forming relatively large holes as shown in
left, and 5.48 wt.% at 600 C, which ought to be the addition of Fig. 2b.
some unknown impurities in the sample during TGA testing. One of the major problems in the development of anode-
However, the conductivity properties of the YSZ films appear supported SOFC is the flatness of the cell due to the very
not to be largely influenced by the impurity in the ethyl cellulose, different sintering profile of the Ni/YSZ substrates and the YSZ
as can be seen in Table 1. In the case of the as-prepared single- thin films. In this study, after co-sintering, the bilayers show
layered green film, a mass loss of 52.5 wt.% occurs after baking somewhat positive curvature towards the electrolyte side due to
at 80 C, which should be due to the removal of terpineol; 61.1 the higher sintering shrinkage of YSZ films. The more the
and 61.5 wt.% at 150 and 180 C, respectively. The mass is quite spinning number, the more positive the curvature. On the other
similar between 150 and 180 C, indicating total removal of the hand, the curvature of the cell based on the 14-m-thick elec-
terpineol in the film. So it is concluded that terpineol can be trolyte film in the present study is slight enough to allow the
entirely removed before 180 C in the newly coated film, following processing e.g., cathode coating and cell sealing to be
while ethyl cellulose begins to burn out after 180 C. As a carried out. Besides lowering the film thickness, sintering
matching of the cells could be obtained by adjusting the pre-
Table 1 firing temperature or thickness of the anode supports [16], etc.
Resistance distribution of the cell from 550 to 700 C
Temperature Ohmic resistance, Electrode polarization The ratio of 3.2. Electrochemical testing results
(C) Ro ( cm2) resistance, Ra + Rc Ro vs. total
( cm2) resistance (%) Fig. 4 depicts the performance of a three-layered film cell
700 0.14 1.54 8.50 with the cathode exposed to the stationary air, as shown in
650 0.22 1.62 12.0 Fig. 2d. The cell produces OCVs of N1.10 V in the operating
600 0.36 1.77 16.9 temperature range, showing that the electrolyte film is fully
550 0.65 3.02 17.6
dense and crack-free. The cell yields maximum power densities
 K. Chen et al. / Solid State Ionics 177 (2007) 34553460 3459

of 634, 493, 316, 174 and 86 mW/cm2 at 700, 650, 600, 550 and
500 C, respectively. This result is higher than that of the
supported YSZ film cell with the same SDC-impregnated LSM
cathodes by Yoon et al. (530 and 190 mW/cm2 at 750 and
650 C, respectively) [6]. Moreover, this result is also
comparable with that of the low temperature SOFCs based on
a Gd-doped ceria (GDC) film (380 and 140 mW/cm2 at 600 and
500 C, respectively) [17], indicating the potential application
of the high temperature electrolyte material YSZ to low temp-
erature SOFCs.
At high current densities, the IV curves show somewhat
negative curvatures at 700 and 650 C. Concentration polar-
ization usually associated with the negative curvature should be
induced by the relatively dense cathode layer, as can be seen
Fig. 6. Impedance spectra under open-circuit conditions.
from the SEM image in Fig. 2d. This also could be proved by
the result in Fig. 5, which gives the IV and IP characteristics
of the cell at 650 C with the cathode exposed to the stationary better cell performance could be obtained due to the improved
air and to the oxygen with different flow rates, respectively. At cathodes.
high current densities, the cell voltages related to a specific Impedance spectra of the single cell measured under open-
current density are significantly affected, indicating that the cell circuit conditions between 550 and 700 C are shown in Fig. 6.
performance is governed by the mass transfer process of the The total resistance can be divided into ohmic and electrode
cathode as well as interfacial electrochemical reaction and polarization resistance, and the distribution is depicted in
ohmic polarization [18]. The maximum power density, in Table 1. Both of the resistances increase with the decrease in the
consequence, is increased from 493 to 658 mW/cm2 when the operating temperature, so does the ratio of ohmic resistance in
cathode is directly exposed to the open air and to the 100 mL/ the total resistance. The ohmic resistance accounts for just a
min oxygen airflow, respectively. The cell performance small part of the total resistance, which demonstrates that the
increased by 33% due to the improved cathode performance. output performance is dominated by the electrode polarization.
Relatively dense cathodes in this study are probably induced It is known that the electrode polarization resistance is
by the excessive impregnation of the SDC amount into the LSM dominated by the cathode polarization [20], and it is thus
structures, which consequently reduces the cathode porosity. desirable to lower the cathode polarization. The electrode
However, ion impregnation process is an effective way to im- polarization resistance in our study is 1.54 cm2 at 700 C,
prove the cathode performance and a most potential way to get a which is two times more than that of the result in Jiang et al.'s
high cell performance due to its unique characteristics, e.g., by report [19], demonstrating the potential decrease of the cathode
impregnation of ionic conducting-type Gd0.2Ce0.8(NO3)x solu- resistance in our following studies. Murray et al. [21] studied
tion, the electrode polarization resistance of the impregnated the La0.6Sr0.4Co0.2Fe0.8O3 (LSCF)-Ce0.8Gd0.2O3 (GDC) com-
LSM electrodes decreased to 0.72 cm2 as compared to posite cathodes on YSZ electrolytes, and found that addition of
26.4 cm2 for pure LSM electrodes [19]; Yoon et al. [6] found 50 vol.% GDC to LSCF resulted in the cathode polarization
that the poor cell performance with the pure LSM cathode could resistance as low as 0.01 cm2 at 750 C and 0.33 cm2 at
be greatly improved by using SDC-impregnated LSM cathode. 600 C. This is an amazing result, encouraging the researchers
So we believe that by optimizing the impregnation process, a who are devoting to low temperature SOFCs based on YSZ
electrolyte. So it is believed that by optimizing the cathode
fabrication process or utilizing other high performance cathode
materials, better cell performances could be obtained in the
further investigation.

4. Conclusion

Through optimizing the two key processing factors of the

slurry spin coating method, dense and crack-free YSZ thin films
were successfully fabricated on the Ni-YSZ anodes. The result
showed that baking at 400 C for 10 min during the films
preparation procedure for each green coating, the organic ad-
ditives could be removed. Under this heating condition, the
defects in the electrolyte films could be repaired by the
repetitive coating, as long as two or more layers were coated.
Fig. 5. Electrochemical characteristics of the cell when the cathode was under The cells based on three-layered YSZ films were considered to
different gas conditions. have reached the balance of a reasonable thickness and gas-
3460 K. Chen et al. / Solid State Ionics 177 (2007) 34553460

tightness of the electrolyte. With dry hydrogen as the fuel and [5] Z. Cai, T.N. Lan, S. Wang, M. Dokiya, Solid State Ionics 152153 (2002)
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