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Anode supported micro-tubular SOFC fabricated

with mixed particle size electrolyte via phase-
inversion technique

Siti Munira Jamil a,b, Mohd Hafiz Dzarfan Othman a,b,*,

Mukhlis A. Rahman a,b, Juhana Jaafar a,b, Ahmad Fauzi Ismail a,b
a
Advanced Membrane Technology Research Centre, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor,
Malaysia
b
Department of Energy Engineering, Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia,
81310 UTM Johor Bahru, Johor, Malaysia

article info abstract

Article history: Cerium-gadolinium oxide is a promising material for electrolytes of intermediate tem-
Received 6 October 2015 perature solid oxide fuel cells (IT-SOFCs) due to its high electrical conductivity at relatively
Received in revised form lower temperatures of 400e700
C. However, a high sintering temperature of up to 1550
C
28 April 2016 is typically required to produce dense CGO electrolyte, eventually leading to an interfacial
Accepted 3 May 2016 interdiffusion between the electrolyte and electrode components as well as generate a
Available online xxx highly resistive interface which reduces ionic conductivity. Lowering the sintering tem-
perature of the electrolyte will greatly benefit the fabrication of SOFCs. This study exam-
Keywords: ines the effectiveness of introducing nano size CGO particles as an approach to get dense
CGO CGO electrolyte at lower sintering temperature. A series of dope suspensions with 0e50%
Nano size nano size loading were prepared to observe rheology and measure viscosity. Then, 30%
MT-SOFC loading was selected and casting into flat sheet via phase-inversion technique. The flat
Sintering temperature sheet was characterized by morphology, surface roughness and mechanical strength tests.
Particle size The suspension was extruded into dual-layer hollow fiber (DLHF) as well. The electrolyte/
Dense anode dual-layer hollow fibers (DLHFs) half-cell of micro-tubular solid oxide fuel cells (MT-
SOFCs) were prepared via phase inversion based co-extrusion/co-sintering technique. The
developed half-cell was characterized by morphological and gas tightness tests which
further compared them with fully micron ones. The results show that the incorporation of
30% nanoparticle yielded to dense and tight CGO layers sintered at temperature 1450
C,
which about 50
C lower than those reported previously for 100% micron particles. The IeV
measurements demonstrated the maximum power density of 0.66 Wcm2 at temperatures
500
C using 100% H2 as fuel. Therefore, this approach is able to reduce the energy cost for
the microstructural control of the prepared fiber and thus is recommended for the fabri-
cation of low-cost dual-layer hollow fiber micro tubular SOFCs.
2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: hafiz@petroleum.utm.my (M.H.D. Othman).
http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
0360-3199/ 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4
Introduction
Cerium-gadolinium oxide (CGO) is one of the most promising
electrolyte materials for intermediate temperature solid oxide
fuel cells (IT-SOFC) because of its high electrical conductivity
at 500e700
C [1e5]. CGO powders synthesized by mechano-
chemical method were normally sintered at 1550
C to get a
relative density of 95% [6] which ultimately increases the cost
and complicates the cell fabrication process. Moreover, sin-
tering of the layers at temperatures too high to obtain full
densification of the electrolyte layer may cause an interfacial
interdiffusion between the electrolyte and electrodes mate-
rial, eventually generating a highly resistive interface that
may diminish the ionic conductivity [7]. It should be noted
that high sintering temperatures might reduce the porosity in
the electrodes layers [8], particularly in the co-sintering step
[9]. Therefore, densification of CGO electrolyte at lower tem-
peratures has recently become the main focus of SOFC
research.
Theoretically, there are several factors that can influence
the sintering behavior and densification of ceramic particles.
These factors include size and shape of the powder particles,
the porosity and initial density of the body, as well as chemical
factors such as dopant content, impurities, and sintering ad-
ditives [10e13]. Recently, it has been reported that introducing
metal oxides as the sintering additive can may reduce the
sintering temperature of CGO up to 900e1200
C [14e16].
Indeed, in our previous study, we managed to produce a dense
CGO flat sheet at 1400
C, in which the precursor was prepared
by phase-inversion technique [17]. On the other hand, suc-
cessful attempts of CGO sintered at 1250e1400
C has been
reported by introducing nano size particle of CGO as the
starting powder which was achieved using pressing technique
[10,18e22]. As the small particles size exhibit high driving
force [23], it is hypothesized that nano size powders enhance
densification at lower temperature.
The effect of nano size particles was effectively proven
where a high densification of CGO pellet was produced at
1000
C sintering temperature [19]. The weak agglomerates
and high-crystallinity nano powders synthesized by simple
synthetic methods facilitated the densification process. Ruez
et al. [21] reported that their nano-powder possesses excellent
sinterability at low temperatures (1250
C) and short times
(<1 h). Other than that, Gil et al. [18] effectively co-sintered
nano size CGO electrolyte layer that was dip-coated on the
NiO-CGO anode support at temperature 1300
C with 98%
relative density and ~10 mm thickness. Glasscock et al. [10] was
successfully sintered the CGO pellet at 1400
C with the used
of nano size CGO as starting powders. However, the effec-
tiveness of this approach depends on the fabrication tech-
nique itself.
Currently, phase inversion-based extrusion has been one
of the most promising techniques for the fabrication of
micro tubular SOFC [24]. The significant advantage given by
the phase inversion process is that it provides the ability to
control the internal structure of the hollow fiber. Never-
theless, most literature studies have reported the signifi-
cant of introducing nano size particles in pressing
technique. To the best of the author's knowledge, no study
Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
has been conducted using phase inversion technique
particularly in preparing the electrolyte with different par-
ticle size for MT-SOFCs application. Realising the huge po-
tential that is offered by phase inversion technique, it is
relevant to implement an approach for reducing the sin-
tering temperature by using nano range powders and un-
derstanding how it affects the microstructure and
densification temperature.
The preparation of the electrolyte suspension via phase
inversion technique could be more complicated when it in-
volves the incorporation of nano size particles. The sus-
pension with good dispersion of nano size powders are
difficult to realize and agglomeration is expected for high
surface area powders. The suspension for phase inversion
technique was not able to be prepared from the nano size
particles alone; instead, the nano size particles should be
blended with the micron size particle [25]. Therefore, in
order to study the effect of nano particle size loading on the
sintering behavior analysis of CGO, a series of dope sus-
pension with different ratio between nano and micron par-
ticles of CGO; which is between 0% and 50% nano size
loading have been prepared. Both rheology and viscosity of
the suspensions were observed. Hence, 30% loading was
selected and casting into flat sheet via phase-inversion
technique. The flat sheet was characterized by
morphology, surface roughness, and mechanical strength
tests. A suspension was extruded into dual-layer hollow
fiber (DLHF) as well. The electrolyte/anode DLHF as half-cell
of micro-tubular solid oxide fuel cells (MT-SOFCs) has been
prepared via a phase inversion based co-extrusion/co-
sintering technique. The developed half-cell was character-
ized by morphological and gas tightness tests which further
compared with fully micron ones. Finally, cell performance
was measured at 500
C using H2 as fuel.
Experimental
Materials
Commercially available micron size CGO (surface area
12 m2 g1, particle size 0.1e0.4 mm d50) and nano size
CGO (surface area 192 m2 g1, particle size 60 mesh d50) and
nickel oxide (NiO, surface area 5 m2 g1, d50 0.55 m) were
purchased from NexTech Materials Ltd. and was used as
supplied. Polyethersulfone (PESf) (Radel A-300, Ameco Per-
formance) and polyethyleneglycol 30-dipolyhydroxystearate
(Arlacel P135, Uniqema) was used as a polymer binder and
dispersant, respectively. N-methyl-2-pyrrolidone (NMP) (AR
Grade, Qrec) was used as the solvents for inner and outer layer
spinning suspensions and tap water was used as the external
and internal coagulants, respectively.
Dilatometry and particle analyses
The sintering behaviors of the micron size and nano size
ceramic materials were studied using a dilatometer (Leinsis,
model L75104). For the purpose of dilatometry testing, the
mixtures of the ceramic powders were pressed into rectan-
gular bars with the dimensions of 6 mm  6 mm  20 mm for
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4 3

testing. Measurements were carried out under static air at-
mosphere, using a heating rate of 10
C/min from room tem-
perature to 1500
C.
Nitrogen adsorption/desorption measurement was per-
formed at 196
C using Micromeritics instrument (3Flex
Version 3.01). Measurements were performed in the relative
pressure range from 0.03 to 0.99. The classic relative pressure
range (P/P0 0.05 to 0.30) was chosen to determine the BET
(BrunauereEmmetteTeller) specific surface area. The
adsorption/desorption isotherms were used to calculate the
pore size distributions with BJH (Barret, Joyner, Halenda)
method.
Suspensions and flat sheet preparation
During the suspension preparation, the ceramic powders was
first mixed with solvent and the dispersant and stirred for
48 h. Then, polymer binder was gradually added into the
mixtures under stirring. Mixing was carried out for an extra
48 h to obtain homogeneous spinning suspension. Suspension
compositions are shown in Table 1.
Prior to casting, the electrolyte suspension was stirred at
room temperature to degas for 1 h. The suspension was
then casted on a glass plate using glass rod to form a thin
film. Viscosity data was collected at shear rates between
0 and 100 s1 at 27
C using Brookfield PVDV-I Prime
viscometer (concentric cylinder geometry) whereas spin-
ning suspension samples were taken and tested immedi-
ately prior to flat sheet preparation. The suspension was
transformed to the flat sheet via casting procedure on a
glass plate. Then, the flat sheet was dried in an ambient
drying for 4 h. Then, the flat sheet was immersed in tap
water overnight. Lastly, the membrane was detached from
the glass plate.
extrusion process. Prior to co-extrusion, all spinning sus-
pensions were degassed at room temperature under stirring
to fully removes the air trapped inside the suspensions. The
spinning suspensions were then loaded into a stainless steel
container and forced through a triple-orifice spinneret as
shown in Fig. 1.
The extrusion rates of the inner and outer layers were
accurately monitored and controlled by syringe pumps (PHD
2000 Programmable, HARVARD APPARATUS). The operating
conditions employed for preparing the anode/electrolyte
dual-layer HFs are summarized in Table 2. The resultant
hollow fiber precursors were then co-sintered in a tube
furnace XY-1700, Magna Value. The temperature was
increased from room temperature to 400
C at 5
C/min for
1 h, then to 800
C at 5
C/min for 1 h and finally to target
temperature (i.e. 1300, 1400 and 1500
C) at 10
C/min for 12 h.
The temperature was then reduced to room temperature at
5
C/min. During these fabrication stages, several parameters
were varied, such as extrusion rate and co-sintering tem-
perature, in order to optimize the structure of dual-layer
hollow fiber.
Characterizations of flat sheet
In order to determine the properties of samples, the flat
sheet was characterized using a number of analyses. The
morphology of the flat sheet was examined using a TM3000,
Hitachi scanning electron microscopy (SEM) at an acceler-
ating voltage of 15 kV. The flat sheet was snapped in order to
obtain cross-sectional fracture. Then, these flat sheet

Preparation of NiO-CGO/CGO dual-layer hollow fibers

In the preparation of the anode/electrolyte dual-layer hollow

fibers, two ceramic suspensions were separately prepared.
The suspension of anode layer was composed of 60wt% of
NiO and 40wt% of CGO micron size. The selection of ceramic
composition of NiO60-CGO40 (precursor composite for Ni-
CGO anode) support was decided on the basis of their prac-
ticality in potential use as an anode of half-cell for IT-SOFC
[9,11,26,27]. The electrolyte layer compositions are based on
30% nano size loading. The suspension of the inner layer was
composed of the anode materials and the outer layer con-
tains electrolyte material. The dual-layer hollow fiber pre-
cursors were prepared via the phase inversion-based co-

Table 1 e Suspension composition of modified CGO.

Sample CGO micron CGO nano PESf Arlacel NMP
size size P135
N-0 58.00 e 5.80 0.12 36.08
N-10 52.20 5.80 5.80 0.12 36.08
N-20 46.40 11.60 5.80 0.12 36.08
N-30 40.60 17.40 5.80 0.12 36.08 Fig. 1 e Schematic diagram of the phase inversion-based
N-40 34.80 23.30 5.80 0.12 36.08 co-extrusion process of the dual-layer hollow fibers
N-50 29.00 29.00 5.80 0.12 36.08
precursor [28].

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4

Table 2 e Co-extrusion conditions of the hollow fibers.

Air Internal coagulant Inner layer Outer layer
gap injection rate (ml/ extrusion rate extrusion rate
(cm) min) (ml/min) (ml/min)
20 10 7 2e4

samples were placed on a metal holder and sputtered by

gold under vacuum. High-resolution images of the cross-
section of the flat sheet were taken at different magnifica-
tions. Roughness of the sintered surface and pore size dis-
tribution of the sintered flat sheet was investigated using an
XE-100 Park System, an atomic force microscope with SSS-
NCHR non-contact probes at a 1 mm s1 scan speed. Each
flat sheet was snapped into small pieces and placed on the
sample holder. The mechanical strength of flat sheet was
examined by three-point bending test using an Instron
Fig. 2 e Experimental apparatus of single micro-tubular
Model 5544 tensile tester provided with a load cell of 1 kN.
SOFC reactor [28].
The flat sheet was fixed on the sample holder with a 30 mm
distance.
Netherlands) for measuring the voltageecurrent perfor-
Characterizations of dual-layer hollow fiber mances of the micro-tubular SOFCs, with controlled flow rates

The morphology of the dual-layer hollow fibers was exam-

ined using a TM3000, Hitachi scanning electron microscopy N-0
N-20
(SEM) at an accelerating voltage of 15 kV in the same way as 2 (a) N-30
the flat sheet. Meanwhile, the gas-tightness of the electrolyte N-40
0
was determined by pressure change over time using a pres-
sure transducer that was connected to the permeation sys- -2
tem. Nitrogen (N2) was used as a testing gas. Gas permeability
was obtained based on the cylinder pressure change with
dL/L (mm/mm)

-4

time:
-6
 
Vc Po  Pa
P ln (1) -8
RT$At Pt  Pa

where P is the permeability of the test membrane -10

(mol m2 s1 Pa1); VC is the volume of the test cylinder (m3); R
-12
is the gas constant (8.314 J mol1 K1); T is the measured
temperature (K); po and pt are the initial and final measured 0 200 400 600 800 1000 1200 1400 1600

pressures in the test cylinder (Pa); pa is the atmospheric Temperature ( C)

pressure (Pa); A (m2) is the hollow fiber area that is
A [p(Do  Di)L]/ln(Do/Di), where Do and Di are respectively
the outer and the inner diameter of the hollow fiber (m); L is
20
(b)
the length of the hollow fiber (m); and t is the time for mea- 0

surement (s).
-20

N-0
MT-SOFC performance test -40 N-20
dL/dt (mm/min)

N-30
-60 N-40
Prior to the fuel cell test, a cell reactor must be prepared.
Conductive wire as a current collector of the cathode was -80
wrapped around the cathode and conductive silver paste was
-100
used to improve the connection of the wire to the cathode
surface. Another silver spiral wire was inserted inside the fiber -120
lumen to collect the current from the anode. The resultant
-140
micro-tubular SOFC was fixed in a gas-tight aluminium tube
0 200 400 600 800 1000 1200 1400 1600
using a cement sealing paste after applying current collectors
Temperature ( C)
and the example of the fuel cell reactor can be seen in Fig. 2.
The current collection wires was connected to a potentiostat/ Fig. 3 e (a) Sintering curves and (b) sintering rate curves of
galvanostat (Software NOVA 1.5, Autolab, Eco Chemie, electrolyte materials (heating rate 10
C/min).

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4 5

Fig. 4 e Particle rearrangements during sintering.

of hydrogen fed to the anode and oxygen to the cathode at
500
C.
Results and discussion
Particle behavior
Dilatometry data is required for determining the suitable
compositions of electrolyte layer with appropriate sintering
profile. However, it should be kept in mind that the dilatom-
etry measurements were performed on powder pellets and
not on the flat sheet; hence, these values are roughly
approximated. The results of the dilatometry measurement of
samples with 0%, 20%, 30%, and 40% CGO nano size loading
are shown in Fig. 3. When compared with the 0%, 20%, and
40% CGO nano loading, the sample with 30% CGO nano size
loading started to shrink at lower temperature at around
700
C (Fig. 3(a)).
This may be attributed to different particle packing or
packing configuration due to the difference in particle size
distribution resulting from the mixing fraction of CGO pow-
der. A schematic diagram of the particle rearrangement is
shown in Fig. 4. As can be seen, when nano CGO particles are
mixed with micron CGO particles, the resultant powder
mixture has a wider particle size distribution. In this way,
nano size CGO particles are filled to the interstices among
micron CGO particles, resulting in denser packing. Conse-
quently, the rearrangement of particles during sintering step
will simply occur. Thus, the increase in the rate of grain
growth and coarsening is expected could produce a dense
and tight electrolyte layer at lower sintering temperature.
Based on this hypothesis, N30 will therefore achieve the
optimal packing configuration as it shrinks earlier than the
others.
Moreover, the BET surface area, total pore volume and
average pore diameter are tabulated in Table 3. The N2
adsorption/desorption isotherm and corresponding pore size
distribution curves for the electrolyte powders are shown in
Fig. 5. It was observed that the BET surface area of the
electrolyte powders were increased from 9.71 to 174.24 m2/g,
as the nano size loading increased up to 40%. It is certain
that incorporation of nano size particles led to the increase
of surface area [29]. However, when the nano size loading
increased up to 50%, the BET surface area decreased to
86.89 m2/g. Previous study suggested that there is a strong
possibility that agglomeration occurred [30]. Agglomeration
indicates the tendency of clusters of particles adhered
together by surface forces, a sold bridge, or by a liquid. Ag-
glomerates are unfavorable because it can reduce the par-
ticle packing density and promote inhomogeneous dope
suspension and microstructure in the precursor, making it
difficult to achieve the desired final microstructure of high
density.
Furthermore, a narrow pore size distribution for all six
samples with average pore diameter ranging from ~4 to
~40 nm (~40 to ~400
A) are presented in the inset of Fig. 5(a)e(f)
and summarized in Table 3. The results suggested that the
electrolyte powders developed mesoporous characteristics
(2e50 nm), which could mainly be attributed by the numerous
gaps within the CGO lattice [31,32]. As shown in Fig. 5(a)e(d)
and (f), the CGO powders were found to be type IV (based on

Table 3 e Powder characteristics.

Characteristics Surface area Pore volume Pore size
*BET *BJH adsorption BJH desorption BJH adsorption BJH desorption BJH BJH
surface cumulative cumulative cumulative cumulative adsorption desorption
area surface area of surface area of volume of pores volume of pores average pore average pore
(m2/g) pores (m2/g) pores (m2/g) (cm3/g) (cm3/g) width (nm) width (nm)
N-0 9.71 6.30 6.88 0.04 0.06 22.8 35.8
N-10 12.35 9.98 10.05 0.03 0.04 12.0 16.6
N-20 14.37 11.61 12.00 0.03 0.04 11.2 13.9
N-30 54.51 42.81 43.60 0.11 0.13 10.6 11.7
N-40 174.24 158.49 178.44 0.16 0.17 4.1 3.8
N-50 86.89 70.15 72.68 0.17 0.19 9.7 10.6
*
BET Brunauer-Emmett-Teller; BJH Barret, Joyner, Halenda

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4

IUPAC classification) isotherms for the typical H3 hysteresis II isotherms which result from unrestricted monolayer-
loop due to the capillary condensation [33], approving the multilayer adsorption on the nonporous solids [36]. This
presence of mesoporous materials in the catalyst channel or may be attributed to the high packing density of the powder as
cages [34,35] except the N40 powder (Fig. 5(e)) represents type the relative improvement in packing density depends on the

(a) 60
Adsorption
(b)
35
Desorption Adsorption
50 Desorption

Volume Adsorbed (cm/g STP)

Volume Adsorbed (cm/g STP)

30

Dv(d) (cm/g)
40 25
Dv(d) (cm/g)

20
30
15

20 10
Pore Diameter ()

10 5
Pore Diameter ()

0
0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/Po) Relative Pressure (P/Po)

(c) 35
(d) 120
Adsorption Adsorption
30 Desorption Desorption
100
Volume Adsorbed (cm/g STP)

Volume Adsorbed (cm/g STP)

25
Dv(d) (cm/g)
Dv(d) (cm/g)

80

20
60
15

40
10
Pore Diameter () Pore Diameter ()

20
5

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/Po) Relative Pressure (P/Po)

(e) (f)
Adsorption 140 Adsorption
120 Desorption Desorption
Volume Adsorbed (cm/g STP)

Volume Adsorbed (cm/g STP)

120
100
100

80 80

60
60

40

40
20

20 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/Po) Relative Pressure (P/Po)

Fig. 5 e N2 adsorptionedesorption isotherms and inset correspond to the BJH pore size distribution of electrolyte powders (a)
N0, (b) N10, (c) N20, (d) N30, (e) N40 and (f) N50.

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4 7

20000
particle size ratio of the large and small particles [37]. When
two sizes are mixed, the smaller particles fill the unoccupied
voids among the large particles. If the proportion of the
smaller spheres is too great, the proportion of large spheres
15000
could reach a stage at which they become closely packed and
the resulting packing is high. For type IV materials, the graphs
Viscosity (cP)

demonstrated that the isotherms were relatively flat (P/

10000
Po  0.6), due to the adsorption of the samples that mostly
occurred in the micropores (pore size < 2 nm). By the increase
of relative pressure (0.6 < P/Po  1.0), the increase in adsorp-
5000 tion ability was caused by the monolayer and/or multilayer
adsorptions of nitrogen molecules on the meso-structure of
the CGO powders [38].
0 Besides, Fig. 6 represents the viscosity data of the sus-
pensions at a shear rate of 2 s1. As depicted in Fig. 6, vis-
N-0 N-10 N-20 N-30 N-40 N-50 cosity increases with the increases of CGO nano size
CGO nano size loading (%) loading. N-0 is a sample without the addition of nano size
CGO powder. Its viscosity value was used as the reference.
Fig. 6 e Viscosity data of the prepared suspensions.

Fig. 7 e SEM cross sections images of N-30 and N-0 flat sheet electrolytes at different sintering temperatures.

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4

Viscosity data for N-10 and N-20 shows a diluted suspen-
sion and not suitable for casting step [25] while N-30 shows
the remarkable viscosity data for dope solution as the value
was almost closed to the N-0 data compared to N-40 and N-
50 which indicated more viscous suspension. These vis-
cosity data are coinciding with the N2 adsorption/desorp-
tion measurement. It has been revealed that a larger BET
surface area of a material could be advantageous to achieve
better adsorption ability [39]. However, in this particular
study, the high surface area material will adsorb more sol-
vent producing high viscosity of dope suspension. If the
viscosity is too high, the suspension will be unflowable and
thus difficult to cast or extrude. Thus, suspension which
contains mixed particles size requires sufficiently great
particle size ratio with optimal packing density to ensure
good rheology of dope suspension and free from particles
agglomeration.
Morphologies, surface roughness and mechanical strength
of flat sheet
The properties of ceramic powder may affect its dispersion
in the suspension and properties of the electrolyte precur-
sor. From the dilatometry, N2 adsorption/desorption
measurement and viscosity results, it is assured that 30%
nano size CGO loading is the best ratio to produce a good
rheology suspension. Hence, the characterization of the flat
sheet was preceded using N30 samples. To further analyze
the effects of nano particle size on the microstructure of
CGO electrolyte, analysis on the cross sections images was
performed using SEM. The precursor from N-30 was sintered
and compared with the N-0 precursors as shown in Fig. 7
whereby the zoomed area was focused at the center region
of the flat sheet. The precursor was sintered at different
sintering temperature ranging from 1350 to 1450
C. Fig. 7(a)
and (b) shows the SEM images of the flat sheet for both N-
0 and N-30 sintered at 1350
C for 12 h. In these images,
newly grown CGO grains were observed. In this image, grain
boundaries were not as easily identifiable as other images
and a single grain has started to form. In Fig. 7(c) and (d), the
flat sheet sintered at 1400
C for 12 h has been shown. The
porosity and pinhole decreased with an increase in sintering
temperature up to 1400
C. Besides, the grain boundaries
have become gradually clear at this temperature especially
in N-30 flat sheet (Fig. 7(d)). This may be attributed to the
existing of nano size particles which demonstrated high
driving force that can increase the rate of densification [23].
Flat sheet sintered at 1450
C for 12 h showed in Fig. 7(e) and

Fig. 8 e AFM images of N30 at different sintering temperature: (a) 1350
C (b) 1400
C (c) 1450
C; (i) 3D view, (ii) height view,
and (iii) lateral size distribution.

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4
(f). By increasing sintering temperature, those single grains
formed at lower temperature (for example at 1350
C) were
combined. While they filled up the porosity, a dense struc-
ture was formed in N-30 flat sheet. The pores and pinholes
of the N-30 flat sheet almost disappeared due to homoge-
neous grain growth. For ceramic membranes, use of higher
sintering temperature typically contributes to improving the
mechanical strength of the membrane, while also
decreasing the porosity and increases the resistance to gas
permeation. Fully dense CGO with no porosity and cracks
are desirable for the electrolytes of solid oxide fuel cells.
Therefore, this flat sheet can be suitable as an electrolyte of
a SOFC [40e44].
Fig. 8 shows the 3-dimensional AFM images of N-30 flat
sheet sintered at different temperatures in the range of
1350e1450
C. The films sintered at 1450
C show a nearly
homogeneous surface with grains of approximately 1 mm,
along with a smaller pore size (Fig. 8(c)). This result is very
important, as a dense electrolyte structure is needed for
applications in SOFC [40e44]. The increase sintering tem-
perature increases the size of the grains of CGO as well.
Grain growth of the N-30 flat sheet is clearly shown in 3-
dimensional images. By raising the temperature, grain
boundaries can be easily distinguished. In addition, it may
be observed that when the temperature increased, small
particles adhered together to form larger grains. This effect
was coincidence with SEM analysis as previously
mentioned.
In Fig. 8a(iii)ec(iii), the roughness histograms at
1350e1450
C sintering temperature were shown. Average
roughness (Ra) is the most important parameter measured
for each sample by the instrument. Roughness of the surface
was dependent on sintering temperature. At first, because of
the particle arrangement during sintering process,
increasing the sintering temperature from 1350
C up to
1400
C decreased Ra from 106.673 nm to 65.164 nm and as a
result, the surface became smoother. However, Ra
50
45
40
Bending Strenght (MPa)
35
30
25
20
15
10
N-0
5 N-30
1340 1360 1380 1400 1420 1440
Sintering temperature ( C)
o layer presented in zoom area images demonstrate that the
Fig. 9 e Bending strength of the flat sheet at different
sintering temperature.
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via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
9
significantly increased from 69.996 nm to 178.0 nm as the
samples sintered at the higher temperatures like 1450
C.
This phenomenon may be attributed to the grain growth
that was begun. In order to achieve the smoothest surface of
the N-30 CGO flat sheet, the sintering temperature should be
optimized. It was recommended that the roughness of in-
terfaces in SOFCs (anode/electrolyte and cathode/electrolyte
interfaces) can significantly influence the electrochemical
characteristics of single cells and conductivity of CGO
electrolyte.
Furthermore, it is expected that a mix particle size of CGO
for the electrolyte layer would reduce the co-sintering tem-
perature needed to densify the CGO layer. In fact, the use of
higher co-sintering temperature in ceramic membrane nor-
mally contributes to improving the mechanical strength of
the membrane, while decreasing porosity and increasing
resistance to gas permeation. It is important to note that the
dual-layer HFs developed in this study is for the construction
of micro-tubular SOFC, which requires reasonably strong
mechanical properties for the deposition of remaining com-
ponents such as cathode and current collector, a highly
porous anode, and a dense electrolyte layer. Consequently,
the mechanical strength of flat sheet sintered at various
temperatures was evaluated in terms of flexural strength via
three-point bending test. The results are presented in Fig. 9.
The reported mechanical strength data are a mean of mea-
surements on 3 samples for each co-sintering temperature.
The figure indicates the mechanical strength gradually
increased as the sintering temperature increased. The me-
chanical strength of the developed N-30 flat sheet sintered at
1450
C for 12 h is about 47.8 MPa. This value is comparable
with the N-0 fiber sintered at the same temperature
(34.5 MPa). This may be due to the increased grain size, with
closer grains generating stronger bonding and thus giving
higher mechanical strength. These results are in agreement
with SEM and AFM results in Figs. 7 and 8. This observation
demonstrates that 30% nano size loading is suitable for
electrolyte preparation via phase inversion technique, better
meeting the requirements for electrolyte suspension
preparation.
Morphologies and electrolyte tightness of dual-layer hollow
fibers
With the best loading of nano size CGO, suspensions were
prepared for dual-layer hollow fiber (HF) fabrication. After co-
sintering the NiOeCGO/CGO precursor fibers and reducing
NiO in the inner layer to Ni, a NieCGO/CGO dual-layer HF for
micro-tubular SOFC can be obtained. The effects of mix par-
ticle size in the electrolyte layer were analyzed as a function of
the co-sintering temperature from 1400
C to 1500
C. The
cross-sections images of the resultant NieCGO/CGO dual-
layer HFs are shown in Fig. 10. The thicknesses of the elec-
trolyte layer were decrease from ca. 61 mm to 24 mm
(Fig. 10(a)e(c)) and ca. 44 mm to 15 mm (Fig. 10(d)e(f)) for N00
1460 and N30 respectively. The microstructures of the electrolyte
layers become denser while the CGO grain size becomes
bigger as the co-sintering temperature increase for both pre-
cursors, N00 and N30. Comparing the microstructure of the
10 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4

Fig. 10 e Cross-section SEM images of the NieCGO/CGO N00 and N30 dual-layer HF at different co-sintering temperatures.

HFs co-sintered at 1500
C (Fig. 10(c) and (f)), the effect of 30%
addition of nano size CGO can be notable as the grain
boundaries are clearly observed in N30 electrolyte layer.
Furthermore, the finger-like voids near the outer surface of
the outer layer became shorter as the co-sintering tempera-
ture increased.
Meanwhile, Fig. 11 shows the outer surface SEM images of
N00 and N30 at different co-sintering temperature. As can be
seen in Fig. 11, the porosity and pinhole of the surface
decreased with the increased of co-sintering temperature up
to 1500
C. Besides, the grain boundaries have become grad-
ually clear at this temperature. Initially, similar trend was
observed for both dual-layer HFs, however the microstruc-
tures are noticeable different at each co-sintering tempera-
ture. The outer surface of both HFs became smoother, but the
average CGO grain size for N00 HF which is visually estimated
are quite smaller compared to the grains size of N30 HF,
approximately 3, 5, and 8 mm for the co-sintering temperature
at 1400, 1450, and 1500
C, respectively.
In addition, the electrolyte layer of SOFC must be imper-
meable to any gas to avoid direct contact between the fuel and
oxidizer. In order to investigate the effect of the co-sintering
temperature on the outer electrolyte layer of the developed
dual-layer HFs, a gas-tightness test was carried out. As seen in
Fig. 12, the nitrogen permeances of the HFs is
20.43  105 molm2s1 Pa1 for N00 and
5 2 1 1
10.75  10 molm s Pa for N30. This value decreases
with the increases of co-sintering temperature. This indicates
that the denser the electrolyte layer, the better the gas-
tightness property of the electrolyte is. These values are
quite a bit lower than those reported in literature [45]. Some
improvement is needed in order to produce a good tightness
property of HFs for MT-SOFCs. However, in this part of study,
dual-layer hollow fiber which co-sintered at 1450
C was

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4 11

Fig. 11 e Outer surface SEM images of the NieCGO/CGO N00 and N30 dual-layer HF at different co-sintering temperatures.

chosen to undergo a performance test with the intention of
achieving the lowest limit of power density that this fiber can
produce.
MT-SOFC performance
A multi-layer cathode consisting of two layers of LSCF-CGO
mixture and one layer of pure LSCF was brush-painted onto
the electrolyte surface of N30 co-sintered at 1450
C. The
electrochemical performance of the full cell with active cell
length of 10 mm, inner diameter of 0.7 mm, and outer diam-
eter of 1.4 mm was investigated at 500
C using hydrogen gas
of 20 cm3 min1 at 20
C, 1 atm at the anode (lumen side) and
oxygen (30 cm3 min1 at 20
C, 1 atm) at the cathode side
(outer surface). Fig. 13 shows the cell voltage and power den-
sity curves as a function of the current density. The open-
circuit voltage (OCV) shows values of ca. 0.65 V at 500
C. A
maximum power density of 0.66 Wcm2 was obtained which
is at par among the data from literature as presented in Table
4. However, the low OCV value indicating that the electrolyte
membrane is not adequately dense for isolating the fuel and
oxidant effectively. Indeed, the low performance of the
assembled SOFC is mainly a result of an unoptimized elec-
trolyte in terms of thickness and tightness. Other than that,
insufficient triple phase boundary (TPBs) and anode catalytic
activity also affect the cell performance. Thus, further modi-
fication is needed in order to improve the performance of the
cell.

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
12 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4

24

Max. Power density (Wcm2)

N0
N30
Permeability x 10 (molm s Pa )
-1
2 -1

0.80
0.58
1.00
0.66
16
-5

OCV (V)
0.90
0.89
0.80
0.65
Temp. (
C)
0
1400 1450 1500

550
570
580
500
Co-sintering temperature (C)

Fig. 12 e Gas-tightness test result of the Ni-CGO/CGO dual-

Fuel stream
layer HFs.

H2
H2
H2
H2
0.7 0.8
0.7

Cell diameter (mm)

0.6
Power density (Wcm-2)

0.6
0.5
Cell voltage (V)

0.5
0.4

1.4
0.8
1.4
1.4
0.4
0.3
0.3
0.2
0.2
0.1 0.1
LSCF-CGO
LSCF-CGO
LSCF-CGO
LSCF-CGO
Cathode

0 0
0 1 2 3 4 5
Current density (Acm-2)
Electrolyte

Fig. 13 e Voltages and power densities as functions of

Table 4 e Comparison of MT-SOFCs performance at 500e600
C.

CGO
CGO
CGO
CGO

current density.
Ni-CGO
Ni-CGO
Ni-CGO
Ni-CGO
Anode

Conclusions
Dual-layer
Dual-layer
Dual-layer
Dual-layer
Layer

The sintering temperature for the production of a dense CGO

electrolyte layer has been successfully lowered by incorpo-
rating nano size CGO. The sintering temperature was low-
Anode-supported
Anode-supported
Anode-supported
Anode-supported
Support design

ered to 1450
C via 30% nano size CGO loading. The loading of
nano size CGO during powder suspension preparation plays
an important role in the densification temperature of the
CGO electrolyte as prepared by phase inversion technique.
Despite this, the powders must achieve optimal packing in
order to produce the desired rheology of electrolyte sus-
Year
2009
2010
2011
2015

pension to be compatible with such a technique. It may be

concluded that the approach of mix particle size electrolyte
as a strategy in reducing the sintering temperature is both
This work

scientifically and technically relevant with an understanding

Ref
[43]
[46]
[27]

on how to synergize between this approach and the fabri-

cation technique.

Please cite this article in press as: Jamil SM, et al., Anode supported micro-tubular SOFC fabricated with mixed particle size electrolyte
via phase-inversion technique, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.016
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e1 4
Acknowledgment
The authors gratefully acknowledge financial support from
the Ministry of Education Malaysia under the Fundamental
Research Grant Scheme (Project Number:
R.J130000.7809.4F282), and Universiti Teknologi Malaysia
under the Research University Grant Tier 1 (Project number:
Q.J130000.2509.05H53). The authors would also like to thank
Research Management Centre, Universiti Teknologi Malaysia
for the technical support.
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