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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
Advanced Membrane Technology Research Centre, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor,
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: (M.H.D. Othman).
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),
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

has been conducted using phase inversion technique

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

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

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),
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
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
(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
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)


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
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
the length of the hollow fiber (m); and t is the time for mea- 0

surement (s).

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

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

Volume Adsorbed (cm/g STP)

Volume Adsorbed (cm/g STP)


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


20 10
Pore Diameter ()

10 5
Pore Diameter ()

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
Volume Adsorbed (cm/g STP)

Volume Adsorbed (cm/g STP)

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



Pore Diameter () 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)

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

Volume Adsorbed (cm/g STP)


80 80




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),
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

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
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/

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),
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Viscosity data for N-10 and N-20 shows a diluted suspen- measurement and viscosity results, it is assured that 30%
sion and not suitable for casting step [25] while N-30 shows nano size CGO loading is the best ratio to produce a good
the remarkable viscosity data for dope solution as the value rheology suspension. Hence, the characterization of the flat
was almost closed to the N-0 data compared to N-40 and N- sheet was preceded using N30 samples. To further analyze
50 which indicated more viscous suspension. These vis- the effects of nano particle size on the microstructure of
cosity data are coinciding with the N2 adsorption/desorp- CGO electrolyte, analysis on the cross sections images was
tion measurement. It has been revealed that a larger BET performed using SEM. The precursor from N-30 was sintered
surface area of a material could be advantageous to achieve and compared with the N-0 precursors as shown in Fig. 7
better adsorption ability [39]. However, in this particular whereby the zoomed area was focused at the center region
study, the high surface area material will adsorb more sol- of the flat sheet. The precursor was sintered at different
vent producing high viscosity of dope suspension. If the sintering temperature ranging from 1350 to 1450  C. Fig. 7(a)
viscosity is too high, the suspension will be unflowable and and (b) shows the SEM images of the flat sheet for both N-
thus difficult to cast or extrude. Thus, suspension which 0 and N-30 sintered at 1350  C for 12 h. In these images,
contains mixed particles size requires sufficiently great newly grown CGO grains were observed. In this image, grain
particle size ratio with optimal packing density to ensure boundaries were not as easily identifiable as other images
good rheology of dope suspension and free from particles and a single grain has started to form. In Fig. 7(c) and (d), the
agglomeration. flat sheet sintered at 1400  C for 12 h has been shown. The
porosity and pinhole decreased with an increase in sintering
Morphologies, surface roughness and mechanical strength temperature up to 1400  C. Besides, the grain boundaries
of flat sheet have become gradually clear at this temperature especially
in N-30 flat sheet (Fig. 7(d)). This may be attributed to the
The properties of ceramic powder may affect its dispersion existing of nano size particles which demonstrated high
in the suspension and properties of the electrolyte precur- driving force that can increase the rate of densification [23].
sor. From the dilatometry, N2 adsorption/desorption 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),
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(f). By increasing sintering temperature, those single grains significantly increased from 69.996 nm to 178.0 nm as the
formed at lower temperature (for example at 1350  C) were samples sintered at the higher temperatures like 1450  C.
combined. While they filled up the porosity, a dense struc- This phenomenon may be attributed to the grain growth
ture was formed in N-30 flat sheet. The pores and pinholes that was begun. In order to achieve the smoothest surface of
of the N-30 flat sheet almost disappeared due to homoge- the N-30 CGO flat sheet, the sintering temperature should be
neous grain growth. For ceramic membranes, use of higher optimized. It was recommended that the roughness of in-
sintering temperature typically contributes to improving the terfaces in SOFCs (anode/electrolyte and cathode/electrolyte
mechanical strength of the membrane, while also interfaces) can significantly influence the electrochemical
decreasing the porosity and increases the resistance to gas characteristics of single cells and conductivity of CGO
permeation. Fully dense CGO with no porosity and cracks electrolyte.
are desirable for the electrolytes of solid oxide fuel cells. Furthermore, it is expected that a mix particle size of CGO
Therefore, this flat sheet can be suitable as an electrolyte of for the electrolyte layer would reduce the co-sintering tem-
a SOFC [40e44]. perature needed to densify the CGO layer. In fact, the use of
Fig. 8 shows the 3-dimensional AFM images of N-30 flat higher co-sintering temperature in ceramic membrane nor-
sheet sintered at different temperatures in the range of mally contributes to improving the mechanical strength of
1350e1450  C. The films sintered at 1450  C show a nearly the membrane, while decreasing porosity and increasing
homogeneous surface with grains of approximately 1 mm, resistance to gas permeation. It is important to note that the
along with a smaller pore size (Fig. 8(c)). This result is very dual-layer HFs developed in this study is for the construction
important, as a dense electrolyte structure is needed for of micro-tubular SOFC, which requires reasonably strong
applications in SOFC [40e44]. The increase sintering tem- mechanical properties for the deposition of remaining com-
perature increases the size of the grains of CGO as well. ponents such as cathode and current collector, a highly
Grain growth of the N-30 flat sheet is clearly shown in 3- porous anode, and a dense electrolyte layer. Consequently,
dimensional images. By raising the temperature, grain the mechanical strength of flat sheet sintered at various
boundaries can be easily distinguished. In addition, it may temperatures was evaluated in terms of flexural strength via
be observed that when the temperature increased, small three-point bending test. The results are presented in Fig. 9.
particles adhered together to form larger grains. This effect The reported mechanical strength data are a mean of mea-
was coincidence with SEM analysis as previously surements on 3 samples for each co-sintering temperature.
mentioned. The figure indicates the mechanical strength gradually
In Fig. 8a(iii)ec(iii), the roughness histograms at increased as the sintering temperature increased. The me-
1350e1450  C sintering temperature were shown. Average chanical strength of the developed N-30 flat sheet sintered at
roughness (Ra) is the most important parameter measured 1450  C for 12 h is about 47.8 MPa. This value is comparable
for each sample by the instrument. Roughness of the surface with the N-0 fiber sintered at the same temperature
was dependent on sintering temperature. At first, because of (34.5 MPa). This may be due to the increased grain size, with
the particle arrangement during sintering process, closer grains generating stronger bonding and thus giving
increasing the sintering temperature from 1350  C up to higher mechanical strength. These results are in agreement
1400  C decreased Ra from 106.673 nm to 65.164 nm and as a with SEM and AFM results in Figs. 7 and 8. This observation
result, the surface became smoother. However, Ra demonstrates that 30% nano size loading is suitable for
electrolyte preparation via phase inversion technique, better
meeting the requirements for electrolyte suspension
Morphologies and electrolyte tightness of dual-layer hollow
45 fibers
Bending Strenght (MPa)

With the best loading of nano size CGO, suspensions were

prepared for dual-layer hollow fiber (HF) fabrication. After co-
30 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-
20 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-
10 layer HFs are shown in Fig. 10. The thicknesses of the elec-
N-0 trolyte layer were decrease from ca. 61 mm to 24 mm
5 N-30 (Fig. 10(a)e(c)) and ca. 44 mm to 15 mm (Fig. 10(d)e(f)) for N00
1340 1360 1380 1400 1420 1440 1460 and N30 respectively. The microstructures of the electrolyte
Sintering temperature ( C)
o layer presented in zoom area images demonstrate that the
layers become denser while the CGO grain size becomes
Fig. 9 e Bending strength of the flat sheet at different bigger as the co-sintering temperature increase for both pre-
sintering temperature. cursors, N00 and N30. Comparing the microstructure of the

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),
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% approximately 3, 5, and 8 mm for the co-sintering temperature
addition of nano size CGO can be notable as the grain at 1400, 1450, and 1500  C, respectively.
boundaries are clearly observed in N30 electrolyte layer. In addition, the electrolyte layer of SOFC must be imper-
Furthermore, the finger-like voids near the outer surface of meable to any gas to avoid direct contact between the fuel and
the outer layer became shorter as the co-sintering tempera- oxidizer. In order to investigate the effect of the co-sintering
ture increased. temperature on the outer electrolyte layer of the developed
Meanwhile, Fig. 11 shows the outer surface SEM images of dual-layer HFs, a gas-tightness test was carried out. As seen in
N00 and N30 at different co-sintering temperature. As can be Fig. 12, the nitrogen permeances of the HFs is
seen in Fig. 11, the porosity and pinhole of the surface 20.43  105 molm2s1 Pa1 for N00 and
5 2 1 1
decreased with the increased of co-sintering temperature up 10.75  10 molm s Pa for N30. This value decreases
to 1500  C. Besides, the grain boundaries have become grad- with the increases of co-sintering temperature. This indicates
ually clear at this temperature. Initially, similar trend was that the denser the electrolyte layer, the better the gas-
observed for both dual-layer HFs, however the microstruc- tightness property of the electrolyte is. These values are
tures are noticeable different at each co-sintering tempera- quite a bit lower than those reported in literature [45]. Some
ture. The outer surface of both HFs became smoother, but the improvement is needed in order to produce a good tightness
average CGO grain size for N00 HF which is visually estimated property of HFs for MT-SOFCs. However, in this part of study,
are quite smaller compared to the grains size of N30 HF, 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),
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 (outer surface). Fig. 13 shows the cell voltage and power den-
achieving the lowest limit of power density that this fiber can sity curves as a function of the current density. The open-
produce. circuit voltage (OCV) shows values of ca. 0.65 V at 500  C. A
maximum power density of 0.66 Wcm2 was obtained which
MT-SOFC performance is at par among the data from literature as presented in Table
4. However, the low OCV value indicating that the electrolyte
A multi-layer cathode consisting of two layers of LSCF-CGO membrane is not adequately dense for isolating the fuel and
mixture and one layer of pure LSCF was brush-painted onto oxidant effectively. Indeed, the low performance of the
the electrolyte surface of N30 co-sintered at 1450  C. The assembled SOFC is mainly a result of an unoptimized elec-
electrochemical performance of the full cell with active cell trolyte in terms of thickness and tightness. Other than that,
length of 10 mm, inner diameter of 0.7 mm, and outer diam- insufficient triple phase boundary (TPBs) and anode catalytic
eter of 1.4 mm was investigated at 500  C using hydrogen gas activity also affect the cell performance. Thus, further modi-
of 20 cm3 min1 at 20  C, 1 atm at the anode (lumen side) and fication is needed in order to improve the performance of the
oxygen (30 cm3 min1 at 20  C, 1 atm) at the cathode side cell.

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via phase-inversion technique, International Journal of Hydrogen Energy (2016),
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Max. Power density (Wcm2)

Permeability x 10 (molm s Pa )
2 -1


Temp. ( C)
1400 1450 1500

Co-sintering temperature (C)

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

Fuel stream
layer HFs.

0.7 0.8

Cell diameter (mm)

Power density (Wcm-2)

Cell voltage (V)


0.1 0.1

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

Fig. 13 e Voltages and power densities as functions of

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


current density.


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-
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-

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


on how to synergize between this approach and the fabri-

cation technique.

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via phase-inversion technique, International Journal of Hydrogen Energy (2016),
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 13

[13] Han M, Liu Z, Zhou S, Yu L. Influence of lithium oxide

Acknowledgment addition on the sintering behavior and electrical conductivity
of gadolinia doped ceria. J Mater Sci Technol 2011;27:460e4.
The authors gratefully acknowledge financial support from
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Effects of firing conditions and addition of Co on bulk and
Research Grant Scheme (Project Number:
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under the Research University Grant Tier 1 (Project number: j.ssi.2005.06.023.
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