J. Am. Ceram. Soc.
, ]] []]] 1–7 (2009)
Journal
Fabrication and Characterization of Ce0.8Sm0.2O1.9 Microtubular
Dual-Structured Electrolyte Membranes for Application in Solid Oxide
Fuel Cell Technology
Naitao Yang,z,y Xiaoyao Tan,w,y Zifeng Ma,z and Alan Thursfieldz
z
Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
y
School of Chemical Engineering, Shandong University of Technology, Zibo 255049, China
z
School of Chemical Engineering and Advanced Materials, Newcastle University, Newcastle upon Tyne NE1 7RU, U.K.
Samaria-doped ceria (SDC, Ce0.8Sm0.2O1.9) ceramic powders
of submicrometer size were synthesized by a sol–gel auto-com-
bustion method. From these powders microtubes with a dual
structure comprising of a dense layer and a porous substrate
layer were fabricated in a single step through a phase inversion/
sintering technique. A sintering temperature in excess of
14501C is required for SDC to achieve gastight microtubes.
The mechanical strength of the SDC microtubes increases with
increasing sintering temperature and may attain up to 208 MPa
when sintered at 15001C. Electrical impedance spectroscopy
studies indicate that the SDC microtubes have electrical con-
ductivities of 4.46  104–0.072 S/cm and corresponding acti-
vation energy of 81.9 kJ/mol at temperatures between 4001 and
8001C. Full fuel cells were fabricated by coating
Ba0.5Sr0.5Co0.8Fe0.2O3d (BSCF) on to the inner surface and
a Ni-SDC cermet on to the outer surface of the gastight mi-
crotubes to act as the cathode and the anode, respectively. The
resultant BSCF|SDC|Ni-SDC microcells have a stable output
maximum of 106 mW/cm2 at 7501C when hydrogen and air
were used as fuel and oxidant gas, respectively.
I. Introduction
S OLID oxide fuel cells (SOFCs) are considered to be good can-
didates for the next generation of power sources due to: their
high energy conversion efficiency, fuel flexibility that allows a
variety of fuels such as hydrogen, natural gas, methane, gasoline
and other hydrocarbons to be used, high tolerance to fuel im-
purities and the potential to meet environmental requirements
with respect to pollution and carbon emmisions.1–3 Over the last
century attempts at optimizing fuel cell technology have been
reported with work focusing on improving power output and
producing compact designs. Most work has been done on vari-
ants of the planar and tubular geometries in which a number of
fuel-air flow patterns have been developed. The Siemens Wes-
tinghouse coporation tubular SOFC is a leading design based
upon extrusion technology in conjunction with advanced elect-
rochemical vapor deposition processes (EVD). Fabrication us-
ing EVD is however costly and complex but this obstacle may be
overcome by alternatives such as plasma spraying. A recently
published concise text on the state of the art in SOFC technol-
ogy provides a good overview.4 In recent years considerable at-
tention has been paid to microtubular solid oxide fuel cells (MT-
B. Dunn—contributing editor
Manuscript No. 25857. Received February 8, 2009; approved June 8, 2009.
This work was financially supported by the National Natural Science Foundation of
China (NSFC, No.20076025) and National Basic Research Program of China (973 Pro-
gram, No. 2007CB209700).
w
Author to whom correspondence should be addressed. e-mail: cestanxy@yahoo.
com.cn
1
DOI: 10.1111/j.1551-2916.2009.03267.x
r 2009 The American Ceramic Society
SOFCs) because they exhibit many distinct advantages over
other configurations including; facile high-temperature sealing,
rapid start-up and shut-down operation, high structural stabil-
ity, high thermal-shock resistance and high volumetric output
power density.4–16 The intention is to find a variety of applica-
tions such as dynamical fuel cells for the automobile industry
and power sources for portable devices.
MT-SOFCs can be constructed into anode-supported,5–13
cathode-supported,14–16 or electrolyte-supported configurations.17
The nickel-containing anode support presents good catalytic
activity towards the oxidation of hydrogen and hydrocarbon
fuels and allows a thin-coated electrolyte film to be formed on
the supporting anode leading to a reduced electrolytic resistance
loss and high output power density. The cathode-supported
structure exhibits a particularly attractive advantage with re-
spect to the feasibility for current collecting in stacks. However,
the concentration losses in the electrode-supported fuel cells may
become significant because of gas diffusion resistance through
thick electrodes. Furthermore, the thin electrolyte membrane in
such structures is susceptible to mechanical failure due to the
resultant volume change from heating and cooling cycles. The
process to form a thin dense electrolyte membrane on either
the porous anode or the cathode can be a complicated and time-
consuming challenge with imperfections leading to cross cham-
ber leaks with resultant drop in voltage whereas imperfections in
electrodes deposited on an already dense and gas-tight electrolyte
will not have such a high impact on performance.18 Complica-
tions in fabrication such as these render the cost of SOFCs pro-
hibitively high. In comparison the electrolyte-supported SOFCs
have the advantages of high structural stability with high toler-
ance to thermal stress and may be fabricated more easily at lower
cost although the thickness of the electrolyte must be optimized
to minimize the ohmic losses while possessing sufficient mechan-
ical strength to support the electrodes and associated circuitry.19
Recently, an immersion induced phase inversion/sintering
technique has been developed to fabricate ceramic hollow fiber
membranes which possess an asymmetric structure comprising
of dense and porous layers.20–28 The process typically includes
the preparation of a dope solution containing the ceramic
powder, formation of microtubular precursors by pressurizing
the resultant dope solution into a coagulant bath for phase sep-
aration and finally high-temperature sintering. Because the
dense and the porous substrate in such prepared microtubes
are formed in a single step from the same material, they are fully
integrated. Consequently, cracking or the detachment of the
dense film from the porous substrate which often occurs in
common composite membranes can be prevented in high-tem-
perature operations. In addition, the production cost of the mi-
crotubular membranes can be significantly reduced as relatively
inexpensive equipment is required and manufacture is much
simplified. This is especially important for commercial applica-
tions of ceramic membranes.
2 Journal of the American Ceramic Society—Yang et al.
In this work samaria-doped ceria (SDC), which has been ex-
tensively applied as the electrolyte in intermediate-tempera-
ture SOFCs,29–34 gas-tight microtubes with a dual structure
comprising of a dense layer integrated with a porous substrate
were fabricated through the phase inversion/sintering process.
The SDC electrolyte microtubes supported MT-SOFCs were
fabricated by coating Ba0.5Sr0.5Co0.8Fe0.2O3d (BSCF) and Ni-
SDC cermet on the inner and the outer surfaces as the cathode
and anode, respectively. The performance of the resultant MT-
SOFCs was also evaluated at 55017501C with hydrogen as fuel
and air as oxidant, respectively.
II. Experimental Procedure
(1) Materials
Sm(NO3)3  6H2O (AR grade), Ce(NO3)3  6H2O (AR grade)
(both from Qingda Fine Chemical Inc., Yutai, China) were
used as the metallic precursors for the preparation of
Ce0.8Sm0.2O1.9 powders. Citric acid (499%, Ajax fine chemical,
Sydney, Australia) and ethylene glycol [AR grade, Sinopharm
Chemical Reagent Co. Ltd., Shanghai, China] were used as the
complexing agents. Nitric acid and ammonium hydroxide were
used to adjust the pH of the starting solution. Polyethersulfone,
(PESf) [(Radel A-300), Ameco Performance, Alpharetta, GA]
and N-methyl-2-pyrrolidone (NMP) [AR Grade, 499.8%, AR,
Sinopharm Chemical Reagent Co. Ltd.] were used to prepare
the spinning suspension. Deionized water and tap water were
used as the internal and the external coagulants, respectively.
Commercially available NiO, polyvinyl butyral (PVB), and
terpineol (AR grade) were used to prepare the anode cermet
slurry. BSCF powders of surface area 4.6 m2/g and d50o1 mm
(purchased from Praxair Inc., Woodinville, WA) was used as the
cathode of the cell. Ag paste (PC-Ag-8100 supplied by Sino-
Platinum Metals Co. Ltd., Kunming, China) containing 75 wt%
silver of particle size o7 mm was used as the current collectors in
the microtubular fuel cells.
(2) Synthesis of SDC Powders
SDC powders were prepared by a sol–gel auto-combustion
method. Sm(NO3)3  6H2O and Ce(NO3)3  6H2O were weighted
according to the stoichiometric composition and dissolved into
deionized water to form a solution. Citric acid and ethylene
glycol in quantities of 1.5 times the total metal ions, respectively,
were then added under magnetic stirring until they were dis-
solved completely. The pH of the solution was adjusted to be
34 using nitric acid and ammonium hydroxide to avoid pre-
cipitation. The solution was stirred at 801C on a hot plate for
510 h to form a viscous gel. As the temperature was increased
to around 4001C auto-combustion took place to form pale yel-
low ash, i.e. SDC precursor. The SDC precursor was ground
into powders and was subsequently calcined at 7001C for 2 h
a b
Fig. 1. (a) Single Ni-SDC|SDC|BSCF microtubular fuel cells, (b) cross-sectional graph of the microtubular cell, (c) Interface between the anode and the
electrolyte tube, (d) Interface between the cathode and the electrolyte tube. SDC, Samaria-doped ceria; BSCF, Ba0.5Sr0.5Co0.8Fe0.2O3d.
Vol. ]], No. ]]
under an air flow to remove the residual carbon and form the
stable Sm0.2Ce0.8O1.9 oxide. For fabrication of the SDC micro-
tubes, the resultant powders were ball milled for 10 h, followed
by sieving with a 200-mesh sifter.
(3) Preparation of SDC Microtubes
SDC microtubes were prepared from the calcined and ball-
milled powders by the phase inversion and sintering technique.
The detailed preparation procedures are described else-
where.21,22 In this study the spinning suspension consists of
64.3 wt% SDC powders, 7.1 wt% PESf, and 28.6 wt% NMP. A
spinneret of orifice dimensions outer diameter/inner diameter of
3.0/2.0 mm was used to obtain the microtube precursors. Deion-
ized water and tap water were used as the internal coagulant and
the external coagulant, respectively. Sintering was performed in
the temperature range 1200115001C in ambient nonflowing air
atmosphere for 5 h.
(4) Fabrication and Test of Microtubular Fuel Cells
SDC fuel cells were fabricated by the following procedures. A
gastight SDC microtube of length 5 cm was used as the elec-
trolyte support. An anode slurry was prepared by ball milling
overnight the NiO and SDC powders in 4:1 ratio with PVB as
binder and terpineol as solvent. The resultant slurry was coated
onto the outer surface of the SDC microtubes which were then
sintered at 14001C for 2 h to form the electrolyte/anode half cell.
Afterwards a BSCF suspension prepared by ball milling the
BSCF powders with terpineol and PVB for 12 h was deposited
on the inner surface of the anode/electrolyte half cell. Sintering
of the cathode was conducted at 10001C for 2 h to form
complete single cells. As shown in Fig. 1, the thicknesses of
the formed anode and cathode are around 5 and 50 mm, respec-
tively. The effective area of the fuel cells is, Ae ¼ pðDo 
Din ÞL= lnðDo =Din Þ in which Do, Din, and L are the outer
diameter, inner diameter and the length of the electrode-coated
section, respectively, giving around 1 cm2. Silver paste diluted
with ethanol was brush-applied to the top surface of the elec-
trodes as current collectors. Two Ag wires (+0.2 mm) were
adhered to the electrodes in a helical form with Ag paste by
sintering at 8001C to collect and lead out the current. The
microcell was connected to two quartz tubes on both ends
with a Ag-based high-temperature sealant. In the fuel cell mea-
surements, hydrogen (99.9%) was passed through the anode
side at a flow rate of 10 mL (STP)/min and air was fed into the
cell lumen (cathode side) at a flow rate of 20 mL (STP)/min. A
K-type thermocouple was used to monitor the cell temperature.
Before the collection of data the anode was reduced at 7501C
under pure hydrogen atmosphere for 5 h. The current and volt-
age data were collected with a digital multimeter (GDM 8145,
Tucheng, Taiwan) at temperatures from 5501 to 7501C.
c
5 µm
50 µm
2009 Fabrication and Characterization of Ce0.8Sm0.2O1.9 Microtubes for Solid Oxide Fuel Cells
(5) Characterization Methods
Morphology and microstructures of the SDC powders and mi-
crotubes were observed with scanning electron microscopy
(SEM) (FEI Sirion 200, Eindhoven, the Netherlands). Gold
sputter coating was performed on the samples under vacuum
before the measurements. Crystal phases of the SDC powders
and microtubes were determined by X-ray diffraction (XRD)
(Bruker D8 Advance, Karlsruhe, Germany) using CuKa radia-
tion (l 5 0.15404 nm). The microtubes were ground into fine
powders before the XRD measurements. Continuous scan mode
was used to collect 2y data from 201 to 901 with a 0.021 sampling
pitch and a 21/min scan rate. The X-ray tube voltage and current
were set at 40 kV and 30 mA, respectively. The specific surface
area of the SDC powders was measured with Micromeritics
ASAP 2020 analyzer (Norcross, GA) by the multipoint Bru-
nauer–Emmett–Teller (BET) adsorption technique.
Mechanical strength of the microtubes was measured on a
three-point bending instrument (Instron Model 5544, Norwood,
MA) with the crosshead speed of 0.5 mm/min. The bending
strength, sF, was calculated from the following equation:
8FLDo
sF ¼
pðD4o  D4in Þ
where F is the measured force at which fracture takes place and
L the length of the sample, typically 3.2 cm.
Gas tightness of the sintered SDC microtubes was examined
through a gas permeation test that is described in detail else-
where.35 The microtube was glued onto a stainless-steel sample
holder with epoxy resin and then placed in a stainless-steel cyl-
inder. The gas permeance of the microtube was calculated from
the pressure change in the cylinder as a function of time.
The electrochemical impedance spectra (EIS) of the SDC
microtubes were measured between 4501 and 8001C on an
electrochemistry workstation (IM6ex, Zahner, Germany). Silver
paste was painted on both the inner and the outer surfaces of the
microtube sample as electrodes. The sample, with silver wires
attached to the electrodes, was fired at 8001C before measure-
ments were undertaken to insure good bonding. Measurements
were made at intervals of 501C in air over the frequency range of
0.1 Hz to 1 MHz with a superimposed AC signal voltage of
10 mV. The resistance of the lead wires was subtracted by mea-
suring the impedance of a blank cell. Data were collected and
analyzed with ZPlot 2.9c software.
III. Results and Discussion
(1) Morphology of the SDC Powders and Microtubes
Morphology of the SDC powders prepared by the sol–gel auto-
combustion method is shown in Fig. 2. As can be seen from
Fig. 2(a) the combustion products have a fluffy porous struc-
a b
Fig. 2. Scanning electron microscopic micrograph of (a) the combustion samaria-doped ceria (SDC) powders and (b) the sintered and ball-milled SDC
powders for spinning.
3
ture. Such products have to be treated at high temperature to
remove the residual carbon and form the stable Sm0.2Ce0.8O1.9
oxide before spinning into microtubes, otherwise the resultant
microtubes cannot be sintered into dense membranes. After
sintering at 7001C for 2 h, agglomerates were formed contain-
ing SDC particles in the range 3040 nm, as shown in Fig. 2(b).
These agglomerates were broken into smaller particles again
through ball-milling treatment. BET analysis indicated that the
combustion product and the ball-milled SDC powders have sur-
face areas of 31.97 and 4.29 m2/g, respectively. The decrease in
the surface area after sintering also accounts for the fusion oc-
curring during the sintering process.
Figure 3 shows the SEM micrographs of the SDC microtubes
sintered at different temperatures. As can be seen, the SDC mi-
crotubes have a dual structure comprising of a dense layer of 120
mm thickness integrated with a porous substrate of 200 mm
thickness. Such a dual structure is formed in the spinning pro-
cess because of the different precipitation rates occurring within
the nascent microtubes. The rapid precipitation occurring on the
outer surface due to contact with the large quantity of external
coagulant lead to the formation of a microporous structure
while the slow precipitation on the inner surface gives rise to the
(1) macrovoids or the sponge-like pores.36,37 The sintering only re-
moved the organic components but had not changed the general
structure of the microtubes. As the sintering temperature was
increased, the fine powder particles grew into larger ones and the
pores in the microtubes become smaller. When the microtubes
were sintered at 14501C for 5 h, the maximum size of crystallites
was up to 5 mm and the pores in the outer layer disappeared,
making the microtubes completely gastight as displayed in Figs.
3(c)–(e). The gastight property of the microtubes was further
confirmed by an additional gas permeation test in which the ni-
trogen gas permeance through the microtubes was found to be
only around 1.0  109 mol  (Pa  m2)  s1. However, there are
some small holes presented on the inner surface of the micro-
tubes (Fig. 3(d)). Therefore, the inner layer may be considered as
a porous support, and the gas tightness of the microtubes is at-
tributed to the outer dense layer.
(2) Crystal Phase Development
Figure 4 shows the XRD patterns of the ball-milled SDC pow-
ders and the microtubes sintered at different temperatures. As
can be seen, the SDC powders sintered at 7001C exhibit the pure
cubic fluorite structure of CeO2. After the powders were formed
into microtubes the reflections remained and no additional
peaks developed indicating that the cubic fluorite structure had
been preserved without any additional phases produced during
the spinning and sintering process. However, the XRD peaks of
the microtubes have become more intense and narrower com-
pared with those of the original SDC powders. This suggests that
the crystallites in the microtubes have become larger after sinte-
4 Journal of the American Ceramic Society—Yang et al. Vol. ]], No. ]]

1a 2a 3a

500 µm 500 µm 500 µm

1b 2b 3b

100 µm 100 µm 100 µm

1c 2c 3c

5 µm 5 µm 5 µm

1d 2d 3d

10 µm 10 µm 10 µm

1e 2e 3e

10 µm 10 µm 10 µm

Fig. 3. Scanning electron microscopic micrographs of the samaria-doped ceria microtubes sintered at different temperatures (1) 12001C, (2) 13001C,
(3) 14501C, (a) for cross-section, (b) for microtube wall, (c) for dense layer, (d) for inside surface, and (e) for outside surface, respectively.

ring at high temperatures. Furthermore, it was also observed that
the color of the SDC microtubes changed from yellow to brown
as the sintering temperature was increased from 12001 to 14501C.
(3) Mechanical Strength of the Microtubes
Figure 5 shows the mechanical strength of the SDC microtubes as
a function of temperature. When the sintering temperature is
lower than 13001C, the resultant microtubes were found to be too
fragile for testing. As the sintering temperature was raised from
13001 to 14501C, the microtube bending strength increased no-
ticeably from 20 to 202 MPa. However, when the sintering tem-
perature was further increased from 14501 to 15001C, the bending
strength only marginally increased from 202 to 208 MPa. This
suggests that sintering of the SDC microtube primarily occurs
within the temperature range 13001–14501C. The higher sintering
temperature induces more bonding at the grain boundaries and
removal of micropores as shown in Fig. 3, leading to higher me-
chanical strength. Sintering to temperatures higher than 14501C,
does not improve mechanical strength as the microstructure of
the microtubes had not changed noticeably.
(4) Electrical Properties of the SDC Microtubes
Figures 6(a) and (b) show the equivalent circuit of a solid elec-
trolyte half cell and a typical impedance plot for a SDC micro-
2009 Fabrication and Characterization of Ce0.8Sm0.2O1.9 Microtubes for Solid Oxide Fuel Cells 5

a Rb Rgb Re

Cb Cgb Ce
Intensity (a.u.)

1450°C
b 60
1300°C 450°C
40

–Z″ / Ω
1200°C Rgb
Rb
20
powder

20 30 40 50 60
2θ (degree)
Fig. 4. X-ray diffraction patterns of the samaria-doped ceria (SDC)
powders and the SDC microtubes sintered at different temperatures.
tube at 4501C, where Rb, Rgb, and Re represent the grain bulk
resistance (the resistance of leads is negligible), the grain-bound-
ary resistance and the transfer resistance associated with elec-
trode interfaces, respectively and Cb, Cgb, and Ce are the
capacitances due to the grain, the grain boundary and the elec-
trode interfaces, respectively. The effective resistance of the elec-
trolyte includes both the grain bulk and the grain-boundary
resistance, Re 5 Rb1Rgb, which can be determined from the in-
tercepts of the impedance plot on the real axis.29 Figure 7 shows
the complex impedance plane plots of a SDC microtube mea-
sured in air at 4001–8001C. As can be seen, the impedance spec-
tra exhibit the general behavior of solid electrolytes: three
separated features from high to low frequencies corresponding
to the grain bulk resistance, the effect of grain boundaries and
the electrode conduction process. As the temperature increased,
the arcs shifted to the left and became progressively smaller.
This indicates that each type of resistance (stated above) de-
creases with increasing temperature.
From the individual resistances determined above, the con-
ductivities of the SDC microtubes may be calculated by
70 80 90
0
0 20 40 60 80 100 120
Z′ / Ω
Fig. 6. (a) Equivalent circuit of the solid electrolyte measuring half cell,
(b) typical plot of IS measurement for the samaria-doped ceria micro-
tubes at 4501C.
where Ea is the activation energy for conductivity (J/mol), T is
absolute temperature (K) and A is the preexponential factor
S  cm1  K.
It can be seen that the relationship between the effective con-
ductivity of the microtubes can be depicted fairly well with Ar-
rhenius equation (R2 5 0.998). As the temperature was increased
from 4001 to 8001C, the electrical conductivity of the SDC mi-
crotubes increased from 4.46  104 to 0.072 S/cm. The activa-
tion energy for the electrical conductivity obtained from the
slope of the Arrhenius line was found to be 81.9 kJ/mol. These
values are smaller than those obtained for the conventional disk
pellet geometry electrolyte.30 For example, the conductivity at
8001C and the activation energy for the SDC disk pellet are
0.082 and 96.1 kJ/mol, respectively. Such a decrease in conduc-
tivity may have resulted from microvoids present in the electro-
lyte walls because the conductivity of solid electrolyte is
determined not only by the material properties but also by the
microstructure.

1 d
s¼ (2) (5) Performance of the Microtubular Fuel Cells
Rb þ Rgb Ae
Figure 9 shows the voltage and output power density of the
where s is the conductivity (S/cm); d is the microtubular wall NiO–SDC|SDC|BSCF single cell as a function of current den-
thickness (cm), and Ae is the effective electrode area. sity at different temperatures, where pure hydrogen at 10 mL
Figure 8 shows a plot of the conductivities of the SDC mi- (STP)/min and air at 20 mL (STP)/min were used as the fuel and
crotubes against temperature using the Arrhenius equation oxidant, respectively. It can be seen that the open-circuit voltage
(OCV) of the cell decreases from 0.89 to 0.70 V as the temper-
  ature is increased from 5501 to 7501C. This may be attributed to
A Ea
s ¼ exp (3) the internal short circuit current caused by the mixed conduc-
T RT tivity of the SDC electrolyte and the over potentials at the elec-
trode/electrolyte interfaces related to the cell design and
electrode microstructure.30–33 The linear relationship for all
250
the I–V curves implies that the cell’s output is mainly domi-
nated by the ohmic resistance of the SDC electrolyte. As the
temperature was increased from 5501 to 7501C, the maximum
200 power densities of the cell increased from 27 to 106 mW/cm2.
Bending strength, MPa

However, when the temperature is higher than 7501C, the in-

150
crease in output performance by further increasing temperature
would be limited by the enhanced electronic conductivity of the
electrolyte. This suggests that the SDC-based SOFCs should be
100 operated at intermediate temperatures (o8001C). Although the
microtubular cell in this work demonstrated much lower output
50 power densities than the anode-supported disk geometry cell19
due to the large thickness of the electrolyte layer (B120 mm), the
cell gave a stable power output. In fact, no degradation in the
0 output performance was observed while working over a
1250 1300 1350 1400 1450 1500 1550
2-week period in which 12 cycling operations were performed.
Sintering temperature,°C
In order to improve the output performance of the microtubular
Fig. 5. Bending strength of the samaria-doped ceria microtubes as a fuel cells, the thickness of the dense layer of the microtubes has
function of sintering temperature. to be significantly reduced and the porous layer has to be made
6 Journal of the American Ceramic Society—Yang et al. Vol. ]], No. ]]

8.0
800°C
6.0 750°C

–Z'', Ω
700°C
4.0 650°C

2.0

0.0
0 2 4 6 8 10 12 14 16
Z', Ω

60
600°C 550°C
500°C 450°C
–Z'', Ω

40
400°C

20

0
0 20 40 60 80 100 120
Z', Ω
Fig. 7. Impedance spectra of the samaria-doped ceria microtubes measured in air at different temperatures.

into an electrode by impregnating catalysts. Our future efforts
will be concentrated on the preparation of microtubular elec-
trolytes having a very thin dense skin layer (o10 mm) and a
porous layer with larger pores by modifying the spinning/sinte-
ring technique.38
IV. Conclusions
SDC electrolyte microtubular membrane with a dual structure
comprising of a dense layer of 120 mm thickness integrated with
a porous substrate of 200 mm thickness have been fabricated in a
single step through a phase inversion/sintering technique. Sinte-
ring of the SDC microtubes primarily occurs within the tem-
perature range of 13001–14501C. In order to obtain completely
gastight microtubes, the sintering temperature should be higher
than 14501C. The mechanical strength of the microtubes in-
creases with increasing sintering temperature reaching up to
208 MPa when sintered at 15001C. The electrical conductivities
of the microtubes are 4.46  104–0.072 S/cm in the temperature
range of 4001–8001C with an activation energy of 81.9 kJ/mol.
Electrolyte-supported microtubular fuel cells are fabricated by
coating BSCF on the inner surface and NiO–SDC on the outer
1.0 120
750°C
100
Power density, mW.cm–2

0.8
700°C 80
100
Voltage, V

0.6
Conductivity, (T), S.cm–1.K

650°C
60
10 Ea=81.92 kJ mol–1 0.4
40
R2=0.998
0.2
600°C 20
1
550°C
0.0 0
0 100 200 300 400 500
0.1 Current density, mA· cm–2
0.9 1.0 1.1 1.2 1.3 1.4 1.5
1000/T ,K–1 Fig. 9. Performance of the Ni-SDC|SDC|BSCF microtubular fuel cells
with H2/air feed at different temperatures (H2 flow rate 5 10 mL (STP)/
Fig. 8. Conductivity of the SDC microtubes sintered at 14501C as a min, air flow rate 5 20 mL (STP)/min). SDC, samaria-doped ceria;
function of temperature. BSCF, Ba0.5Sr0.5Co0.8Fe0.2O3d.
2009 Fabrication and Characterization of Ce0.8Sm0.2O1.9 Microtubes for Solid Oxide Fuel Cells
surface of the gastight SDC microtubes to act as the cathode and
anode, respectively. The resultant cells exhibit a stable power
density maximum of 106 mW/cm2 at 7501C with pure hydrogen
as fuel and air as oxidant, respectively. In order to improve the
output performance of the fuel cells, the thickness of the dense
layer of the microtubes must to be optimized to reduce the
ohmic losses while simultaneously possessing the requisite me-
chanical strength to support the electrodes. The porous layer
offers the possibility of providing a high surface area to accom-
modate one of the two electrodes.
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