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Advance fuel cells using Al2O3-nNaAlO2 composite

as ion-conducting membrane

Baoyuan Wang a, Shuisong Chen b, Wenjing Dong a, Xunying Wang a,

Liangping Shen a,**, Hao Wang a,*
a
Hubei Collaborative Innovation Center for Advanced Materials, Faculty of Physics and Electronic Science, Key
Laboratory of Ferro & Piezoelectric Materials and Devices, Hubei University, Wuhan, Hubei 430062, PR China
b
Yangtze Valley Water Environment Monitoring Center, PR China

article info abstract

Article history: In present work, we reported an novel oxide-salt Al2O3eNaAlO2 composite, which was
Received 31 January 2018 prepared by mixing Al2O3 and Na2CO3 two phase materials in different weight ratio, and
Received in revised form then sintering at 1100
C. The X-ray diffraction pattern, scanning-electron microscope and
14 April 2018 impedance spectra are applied to characterize the crystal structure, morphology and
Accepted 18 April 2018 electrical properties of the Al2O3eNaAlO2 composite. The Al2O3eNaAlO2 composite as
Available online xxx electrolyte membrane was sandwiched by two pieces of Ni0.8Co0.15Al0.05Li-oxide (NCAL)
electrode layer to construct advanced fuel cell. Optimizing the weight ratio of Al2O3 and
Keywords: NaAlO2, such cell delivered an highest power density of 789 mW/cm2 and an open circuit
Ionic conductivity voltage (Voc) of 1.13 V at 575
C. The superior performance is mainly due to the excellent
Solid oxide fuel cells ion-conducting of Al2O3eNaAlO2 composites and the outstanding catalysis activity of the
Aluminium oxide NCAL eletrodes. The EIS results revealed that the Al2O3eNaAlO2 composite possessed su-
Oxide-salt composite perior ionic conductivity of 0.121 S/cm at 575
C. The interfacial effects between oxide-salt
two phase including space-charge and structural misfit at the interface region dominated
the ion transport for Al2O3eNaAlO2 composite.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

temperature applications [4,5]. Meanwhile, high operational

Introduction
Solid oxide fuel cells (SOFC) are considered as an efficient
strategy to solve energy crisis in view of their unique superi-
ority, involving high output, superior fuel flexibility and
environmental friendliness [1e3]. However, conventional
SOFCs constantly face a major obstacle that the traditional
electrolyte materials yttrium-stabilized zirconia (YSZ) just can
work at temperature as high as 800e1000
C to fulfill sufficient
ion-conducting, making it ill-suited for engaging in low
temperatures result in uncontrollable costs, hindering the
overall availability of SOFC commercialization. To address
this issue, many researchers in the world focused their study
on the development of the substituted electrolyte, which
delivered sufficient ion-conducting at low/intermediate tem-
perature ranges (300e700
C) [6e8]. Speaking of single-phase
materials, the ion-conducting mechanism is normally domi-
nated by the oxygen vacancy. Nevertheless, the fewer
amounts of oxygen vacancy and relevant high activation

* Corresponding author. Youyi Road 368#, Wuhan, 430062, China.

** Corresponding author.
E-mail addresses: soso1979@sina.com (L. Shen), nanoguy@126.com (H. Wang).
https://doi.org/10.1016/j.ijhydene.2018.04.149
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Wang B, et al., Advance fuel cells using Al2O3-nNaAlO2 composite as ion-conducting membrane,
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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 8 ) 1 e9
energy in single-phase materials constrain the resultant
oxide-ion conductivity [9]. Therefore, compositing two-phase
or multi-phase material was developed and considered as
one of the most efficient method to obtain high ionic con-
ductivity at low/intermediate temperature [10,11]. Thirty
years ago (in 1973), Al2O3eAgI oxide-salt composite was
discovered by Liang group, the outstanding work detected that
the cation-conducting of Al2O3eAgI composite was signifi-
cantly enhanced in comparison with pure AgI [12]. Following
this pioneering investigations, cation-conducting materials
made from a variety of oxide-salt composites were succes-
sively developed, including Al2O3eCuCl [13], Al2O3eCaF2 [14],
Al2O3eAgBr [15], Al2O3eLiBr and Al2O3eNaCl [16]. Some other
material attempted as electrolytes for low/intermediate tem-
perature SOFCs are ceria-salt composite materials. Fu and Zhu
had experimentally proved that the ionic conductivity of Gd
doped Ceria (GDC)eLiCleSrCl2 composite is 2e10 times in
comparison to that of pure GDC in the temperature range of
400e600
C [17]. Most studies focus on doped ceria-carbonate
composites [18], the fuel cells fabricated from these materials
can work at lower temperatures, e.g. close 0.3 W cm2 ob-
tained at 400
C and even at a temperature as low as 200
C
[19]. Recent researches revealed that compositing semi-
conductor and ionic materials was an effective approach to
realize super-high ionic conductivity. J. Garcia-Barriocanal
et al. demonstrated that the YSZ/SrTiO3 heterostructures
possessed ionic conductivity up to eight orders of magnitude
enhancement in comparison with pure YSZ [20], and Sang Mo
Yang et al. fabricated vertical nanocolumns consisting of
samarium doped ceria (SDC) and SrTiO3, its ionic conductivity
is one order of magnitude higher than plain SDC films [21]. The
unique merits including high conductivity and enhanced
mechanical strength make the two-phase or multi-phase
composites become a prospective candidate for ion-
conducting membrane in SOFC.
In the present work, we herein developed a novel oxide-
salt Al2O3eNaAlO2 composite, and then applied it as ion-
conducting membrane for advanced SOFC. The Al2O3e
NaAlO2 composite showed an expectedly high electrical con-
ductivity of 0.121 S/cm at 575
C, which resulted in superior
performance for the assembled fuel cell.
Experimental
Al2O3 powders with analytical grade were blended with
Na2CO3 in different weight ratio of 9:1, 8:2, 7:3, 6:4, then the
mixture were calcined at 1100
C for 2 h. The product was
milled thoroughly to gain Al2O3eNaAlO2 composite and used
as electrolyte.
Glycerol and ethanol mixture in 9:1 vol ratio were added
into Ni0.8Co0.15Al0.05Li-oxide (NCAL) powder, and then ground
completely to prepare NCAL paste, which was painted on Ni
foam to form Ni-NCAL layer. Two pieces of Ni-NCAL, applied
respectively as anode and cathode, were sandwiched together
with the Al2O3eNaAlO2 composite. The three layers configu-
ration was then uniaxially pressed under 200e300 Mpa load to
fabricate a cell in disc-type.
JSM7100F (JEOL) field-emission scanning electron micro-
scope (FESEM) was used to observe the morphology of
Please cite this article in press as: Wang B, et al., Advance fuel cells using Al2O3-nNaAlO2 composite as ion-conducting membrane,
International Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.04.149
samples, and elemental distribution were obtained by an
Oxford energy dispersive spectrometer (EDS), which was
equipped on FESEM machine. To character the crystal struc-
ture of sample, the X-ray diffraction pattern was collected by a
Bruker D8 X-ray diffractometer. Thermogravimetric analysis-
analysis (TGA) was performed on Perkin-Elmer 7 series ther-
mal analyzer, with a heating rate of 5
C/min. The electro-
chemical impedance spectrum (EIS) was detected by
electrochemical workstation (Gamry Reference 3000) in open
circuit mode under air condition, a 10 mV AC signal with the
frequency range of 0.1e105 Hz was applied.
The performance of fuel cells was collected from current
density-voltage (J-V) and current density-power density (J-P)
curves using a ITECH8511 instrument. Hydrogen was applied
as fuel with constant flow rate of 150 ml min1, and the
oxidant was air with 150 ml min1 flow rate.
Results and discussion
Fig. 1 presents the XRD pattern of Al2O3eNaAlO2 composite
obtained under different Al2O3/Na2CO3 weight ratios. For the
pure Al2O3 sample, five well-defined diffraction peaks can be
detected at 37.39
, 39.43
, 45.72
, 57.43
and 66.96
, which are
respectively indexed to (311), (222), (400), (422) and (440) planes
of Al2O3, identified to the face-centered g-Al2O3 with spinel
phase according to the JCPDS Files Cards No.77-0396. The
Al2O3eNaAlO2 sample obtained from lower Na2CO3 content
(10%) did not show any clear diffraction peak from Na2CO3. As
the Na2CO3 content increase to 20%, some peaks indexed to
NaAlO2 was appeared. The formation of NaAlO2 can be
expressed as following reaction:
Na2 CO3 /Na2 O þ CO2
Na2 O þ Al2 O3 /2NaAlO2
The sodium carbonate was decomposed into sodium oxide
at high temperature, and then the sodium oxide reacted with
aluminium oxide to generate sodium aluminate. Therefore,
the Al2O3eNa2CO3 composite converted into NaAlO2eAl2O3
pseudobinary systems, which was normally applied as a solid
Fig. 1 e The XRD patterns of the Al2O3eNaAlO2 composite
obtained under different weight ratios.
 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 8 ) 1 e9 3

electrolyte in the sodium-sulfur battery [22e24]. The intensity
of diffraction peak indexed as NaAlO2 became more and more
enhanced as the Na2CO3 content increases, indicating more
NaAlO2 has been generated in these composite. NaAlO2 is a
member of the tridymite family. The fundamental unit in
NaAlO2 structure is AlO4 tetrahedra [25]. The moral ratio of
NaAlO2/Al2O3 for these samples obtained from 10 wt%, 20 wt
%, 30 wt% and 40 wt% Na2CO3 was calculated to be 0.24, 0.63,
1.41 and 4, respectively. Therefore, the five samples can be
expressed as Al2O3-nNaAlO2 (n ¼ 0.24, 0.63, 1.41 and 4).
Moreover, the NaAlO2 concentrations will predominately
determine the electrical performance of the resultant com-
posite as the below analysis.
Fig. 2 shows the SEM images of pure Al2O3 and Al2O3-
nNaAlO2 composites (n ¼ 0.24, 0.63, 1.41 and 4) in powder
form. As shown in Fig. 2 (a), the pure Al2O3 powder presented
sheet characteristic with pore structure and big pore size. As it
can be seen, after compositing with NaAlO2 and treated by
annealing, the pore structures have been significantly elimi-
nated for the Al2O3-nNaAlO2 composite. Moreover, obvious
microstructural evolution can be detected among these
Al2O3eNaAlO2 composite samples. The important difference
in the microstructures was the shape and size of grain and
pores. All the structures consisted of a three-dimensional
network of dense grains. The SEM images suggested that
more spherical particles were packed in the sample with low
NaAlO2 content than that of with high NaAlO2 content.
Moreover, the density of these composites enhanced with the
increase of NaAlO2 contents. This is maybe due to formation
of the melting eutectics between NaAlO2 and Al2O3. For the
4Al2O3eNaAlO2 composite, the pore structure has been
completely disappeared and uniform microstructure and high
density was obtained. Such compact property of is vital for the
powder using as electrolyte membrane in SOFC.
The thermal behavior of samples was recorded at a heating
rate of 5
C/min in air condition. Fig. 3(a) depicts the TGA and
differential thermal analysis (DTA) curves of Al2O3eNa2CO3
mixture (70e30 wt%). Four regions of weight loss can be
categorized in the TGA curve, region I start from room tem-
perature to 200
C, where the composite delivered weight loss
up to 4%. Evaporation of water and decomposition of hy-
droxide physisadsorbed on the surface of powders was
responsible for the weight loss in region I. The second region is
in the range of 200
Ce670
C, the weight maintained almost
unchanged in this region, indicating no decomposition reac-
tion was happened. Region III corresponds to the temperature

Fig. 2 e The SEM images of pure Al2O3 (a) and the nAl2O3eNaAlO2 composites (n ¼ 0.24 (b), 0.63 (c), 1.41 (d) and 4 (e)).

Please cite this article in press as: Wang B, et al., Advance fuel cells using Al2O3-nNaAlO2 composite as ion-conducting membrane,
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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 8 ) 1 e9
Fig. 3 e TGA and DTA plot of the Al2O3eNa2CO3 mixture
(70e30 wt%) (a) and Al2O3-1.41NaAlO2 obtained by 1100
C
sintering (b).
of 670e860
C. TGA curves display a steep weight loss in
accompany with an exothermal reaction from the DTA curve,
which is due to the decomposition of sodium carbonate into
sodium oxide as the previous reports [26,27], and the active
Na2O react with Al2O3 to generate NaAlO2. In the region of
860
C-1000
C, the decomposition and the reaction have been
completed, therefore no weight loss was observed in this re-
gion. Fig. 3 (b) presents the TGA and DTA curves of the Al2O3-
1.41NaAlO2 sample. Due to the evaporation of physisadsorbed
water, a slight weight loss can be detected from room tem-
perature to 150
C and accompany with exothermal phe-
nomenon. The Al2O3-1.41NaAlO2 composite maintained
almost the constant weight in the temperature range of
150e800
C, neither endothermal nor exothermal phenomena
can be observed in the DTA curve, indicating that all the
Na2CO3 has been completely decomposed during the calci-
nation process and no Na2CO3 was remained in the compos-
ite. Moreover, no reaction took place in the composite
between 150
C and 800
C, the Al2O3eNaAlO2 composites
presented promising stability at the fuel cell operation tem-
perature, this is very important for the stability of the
assembled fuel cell.
Fig. 4 (a) gives the cross-section SEM image of the single cell
assembled from Al2O3-1.4NaAlO2 membrane after perfor-
mance operation. Obviously, three-layer structure can be
detected in the cell, where the Al2O3-1.4NaAlO2 membrane as
the inter-layer is sandwiched by two layers of Ni-NCAL elec-
trode. The thickness of electrolyte interlayer and the two
electrode layers are 400 mm and 700 mm, respectively. It can be
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International Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.04.149
found that the Ni-NCAL layer is well contact with the Al2O3e
NaAlO2 membrane and no delamination is observed at the
interface, this may be due to the good thermal expansion
compatibility between Ni-NCAL layers and Al2O3eNaAlO2
membrane. The well-maintained structure of three-layer
configuration after cell operation revealed good mechanical
strength for the device. From the elemental mapping, the
presence of Na, Al and O element for the interlayer confirms
the main component of NaAl-oxide. Homogeneous distribu-
tion of Ni and Co can be detected in the two electrode layers,
indicating the electrode consisted of NiCo-oxide. The signal of
Li element is too light to be revealed, and the Al content in the
NiCoAlLi-oxide (NCAL) is very low, therefore very weak Al
signal are detected in the electrode layers. It is worthily
mentioned that no obvious elemental diffusion was found
during the cell operation.
Fig. 5(a) and (b) reveal the detailed SEM images of Al2O3-
1.4NaAlO2 electrolyte membrane after cell operation. It can be
found that the membrane has relatively promising density,
there is no continuous pores or macro cracks, the gas-tight
structure of the electrolyte membrane can separate the
hydrogen and oxygen to avoid the burst occurring, this point is
determinative for the performance of assembled fuel cell [28].
From Fig. 5(c) and (d), both the anode and cathode layer pre-
sent desired porosity, such microstructure is in favor of
diffusing gas and extending the triple phase boundary. The
NCAL particles in cathode side show an average size of
500 nm, and uniformly cover on the Ni-foam, some big sphere
consisted of agglomerated particles can be found. In anode
area, the particles aggregate more closely, and a remarkable
morphology evolution is observed in comparison with the
cathode particle, this is ascribed to the reduction of NCAL into
metal Ni in hydrogen condition [29,30].
The Al2O3eNaAlO2 composites were pressed under
200e300 Mpa load to fabricate a pellet in disc-type. Both sides
of the pellets were painted with Ag paste, and then calcinated
at 600
C for 30 min to complete the pellet preparation. The EIS
characterization was conducted on the pellets in the tem-
perature range of 400e575
C under air atmosphere. Fig. 6 (a)
shows a typical EIS of the Al2O3-1.41NaAlO2 pellet at 450
C.
Generally, impedance plots of ionic conductors included three
contributions, the arc at high frequencies passing through the
origin attributed to the bulk polarization, and the broad arc at
intermediate frequencies ascribed to grain-boundary
behavior. The third process, i.e. electrode behavior corre-
sponded to one arc at low frequencies. Hence, we used the
equivalent circuit mode of Rb/Rgb(CPE1)/Re(CPE2) to simulate
the raw data on Zview software. Where the Rb represents
grain resistance, determining by the ion-conducting within
grain, and Rgb is the resistance of grain boundaries, which was
derives from the ionic conduction along or across grain
boundaries, both Rb and Rgb contributed to the total re-
sistances of Al2O3-nNaAlO2 composites [31]; Then the con-
ductivity s at different temperatures can be deduced from the
macroscopic sample dimension using the following equation:
L
s¼
SR
where R is the total resistance, S and L respectively denotes
the surface area and thickness of the pellets. The Arrhenius
 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 8 ) 1 e9 5

Fig. 4 e Cross-sectional SEM and corresponding elemental mapping by energy dispersive spectroscopy of a single cell
assembled from Al2O3-1.41NaAlO2 composite after performance test.

plots of Al2O3-nNaAlO2 composite is shown in Fig. 6 (b). Note
that all the samples delivered a ln(sT) 1000/T linear relation
in the Arrhenius curves, suggesting conduction mechanism
has no change in the temperature range of 400
C-600
C [32].
Both NaAlO2 and Al2O3 are dielectric phase with negligible
electronic. Therefore, the electrical conductivity of Al2O3-
nNaAlO2 composite can be deemed as the contribution from
ionic transport [33]. As Fig. 6 presented, the ionic conductivity
for all the samples increased with the temperature raise,
demonstrating a thermally activated process. Moreover, the
ionic conductivity of Al2O3eNaAlO2 composite initially
increased with the NaAlO2 content, and then decrease. The
highest ionic conductivity of 0.12 S/cm was achieved for the
Al2O3-1.41NaAlO2 composite at 575
C. Additionally, the slope
of the Arrhenius plot gave the activation energy (Ea) for ion
transfer based on the Arrhenius equation:
sT ¼ A exp½Ea =ðkTÞ
Here A is a constant, T denotes the Kelvin temperature, k
represents the Boltzmann constant, and Ea is the activation
energy. Consequently, the Al2O3-1.41NaAlO2 composite
revealed a smallest activation energy of 0.82 eV, which is
comparable to the counterpart value of typical electrolyte YSZ
(above 1 eV) and SDC (above 0.8 eV), and belong to the low
activation energy family.
In conventional composite materials the significant con-
ductivity enhancement, so-called composite effect, occurs
usually for a system containing two solid-phase compo-
nents, where one component has a moderate ionic conduc-
tivity while the other is non-conducting. The conductivity
enhancement is suggested to due to the formation of space
charge region and structural misfit at the interface region
between the conducting and the insulating phase [34]. The
composite effect has been observed in many materials [35],
for example, the fluride-Al2O3 composite has high proton
conductivity in hydrogen-containing atmosphere [36]. Tao
and Meng first found that NaCl has both proton and oxygen
ion conduction. The H2/O2 fuel cell using NaCleAl2O3 as
composite electrolyte and platinum as both electrodes
showed a maximum current density of 140 mA cm2 at 720
C
[37]. In addition, doping ceria-carbonate composite is a
typical electrolyte material with ion-conducting

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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 8 ) 1 e9

Fig. 5 e The detailed SEM image of Al2O3-1.4NaAlO2 membrane (a, b), NCAL cathode electrode (c) and NCAL anode electrode
(d) after cell operation.

enhancement [18,19], and compositing semiconductor and
ionic conductor is also a promising strategy for obtaining
desired ionic conductivity [20,21]. In our case, NaAlO2 can be
reduced by hydrogen to form metastable b-alumina, which
posses proton conductivity [38,39]. On other hand, the com-
posite effect was also existed in Al2O3eNaAlO2 system, the
interface between the NaAlO2 particle and Al2O3 phase may
provided fast ionic transport pathway. Thus, we speculated
the Al2O3eNaAlO2 composite is a O2/Hþ dual conductor, this
can be reflected by the water detection on both sides of fuel
cell during operation. The interface between NaAlO2 and
Al2O3 dominated the decent ionic conductivity of the Al2O3e
NaAlO2 composite series. The area of interface region
increased with NaAlO2 content, which resulted in the ionic
conductivity improving with NaAlO2 content at first. Further
increasing the NaAlO2 content, the excessive NaAlO2 will
block the ion conducting, leading to the ionic conductivity
decrease. The highest ionic conductivity of Al2O3-1.41NaAlO2
composite is responsible for the optimal cell performance
and the lowest cell ohmic resistance, which will be presented
as following.
Recent reports indicated that the Ni-NCAL layer can be
utilized as electrodes and can combined with various elec-
trolyte materials to construct symmetrical SOFC, and the
assembled fuel cell delivered desired electrochemical perfor-
mance at low temperature [40e42]. Inspired by this, we chose
two pieces of Ni-NCAL layer as cathode and anode respec-
tively due to its high conductivity, good ORR activity and HOR
activity. Chen reported that the polarization resistances of
NCAL cathode are 0.393 and 0.729 Ucm2 at 550 and 500
C [43],
which is fairly lower than traditional LSCF/GDC cathode
composite [44], indicating that NCAL has good ORR activity.
On the anode side, the NCAL particles on the Ni-foam were
reduced to metal Ni in the H2 atmosphere as our previously
reported [30,45], and metal Ni is a commonly excellent cata-
lyst for H2. Hence, NCAL can function both as anode and
cathode. In addition, a new triple (Hþ/O2/e) conducting
oxide, LiNi0.8Co0.2O2 (NCL) was reported as an excellent cath-
ode material for low temperature SOFC applications, which
possessed improved oxygen reduction activity and extrinsic
proton conductivity [46]. From structural aspect, Ni0.8C-
o0.15Al0.05LiO2-d(NCAL) has identical microstructure as the
aforementioned NCL which is formed by substituting Co3þ
with a small certain amount of Al3þ. Thus, we deduce that the
NCAL is also a triple conducting oxide, and the empirical re-
sults revealed that the NCAL have high electrical conductivity
around 9 S/cm at 500e600
C [45]. The super electrical con-
ductivity made the NCAL layer can work as a good current
collector.
Fig. 7 (a) displayed the J-V and J-P curves of fuel cells with
configuration of Ni-NCAL/Al2O3-nNaAlO2/Ni-NCAL at 575
C. It
can be observed that the NaAlO2 content significantly influ-
enced the open circuit voltage (OCV) and power output of these
assembled fuel cell. As Fig. 7(a) shown, the OCVs initially
increased with NaAlO2 content. When n equaled to 1.41, the
OCV reached the highest value of 1.13 V. Further increasing the
NaAlO2 content, the OCVs maintained constant, and the
Al2O3e4NaAlO2 fuel cell presented almost the same OCV as
that of Al2O3-1.41NaAlO2. Such results can be understood as
following: Fig. 2 revealed that some small particles and pores
was observed in the Al2O3-nNaAlO2 composites when the
NaAlO2 is low (n ¼ 0.24 and 0.63), this may lead to slight gas

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 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 8 ) 1 e9 7

Fig. 7 e Electrochemical performance (a) and Nyquist

curves (b) for the FC fabricated from Al2O3-nNaAlO2
composite (n ¼ 0.24, 0.63, 1.41 and 4.00) at 575
C.

Fig. 6 e (a) The EIS and equivalent circuit of Al2O3-

1.41NaAlO2 pellet at 450
C. (b) Arrhenius plot for electrical ion transport resistance in the electrolyte, electron migration
conductivity of Al2O3-nNaAlO2 composite (n ¼ 0.24, in electrodes and the contact resistance between cell com-
0.63,1.41 and 4). ponents. RO generally equals to the interception with the real
axis at high frequency region. RH at the intermediate/high
frequency zone reflects the charge transfer occurring at the
leakage for the assembled fuel cell. The gas leakage will reduce electrode/electrolyte interfaces. While the contribution of RL
the partial pressure of oxygen, and result in the decrease of in the low frequency range is deemed as the mass transport
OCV according to Nernst equation. Simultaneously, gas resistance, which is related to the process of oxygen molecule
leakage will cause gas combustion and thereby increases the diffusion, absorption and dissociation. The CPE is the con-
local temperature, which cause further decease of OCV [47]. stant phase element that represents a non-ideal capacitor,
When the NaAlO2 content is high, the melting eutectics be- reflecting the double layer capacitance within the catalyst
tween NaAlO2 and Al2O3 displayed high density, the gas layer [48]. The fitting results are collected and list in Table 1.
leakage was eliminated and the OCV presented high value. The RO displays a small value between 0.0788 U cm2 and
When n equaled to 0.24, the maximum power density 0.125 U cm2, suggesting the low ohmic resistance of these
presented a value of 266 mW/cm2. When the NaAlO2 content assembled cells. In addition, the Al2O3-1.41NaAlO2 based fuel
further increased to 0.63, the maximum power output cells presented the lowest RO among all the cells, this
enhanced to 518 mW/cm2. For the sample n ¼ 1.41, an opti- contributed to its optimal electrochemical performance. Be-
mum electrochemical performance with a maximum power sides, the RH of Al2O3-1.41NaAlO2 displayed the smallest
density of 715 mW/cm2 was obtained. This is maybe due to the
highest ionic conductivity and lowest activation energy for
Al2O3-1.41NaAlO2 as Fig. 6 presented. As n increased to 4, the
maximum power density reduced to 629 mW/cm2. Table 1 e The fitting results of impedance spectra.
The EIS curves of these fuel cells fabricated from Al2O3e Sample (n) RO (U cm2) RH (U cm2) CPE1- RL (U cm2) CPE2-
NaAlO2 composite with different NaAlO2 content are tested T T
under fuel cell condition, as Fig. 7(b) revealed. The raw 0.24 0.125 0.074 0.154 0.264 0.818
impedance spectra is simulated by the equivalent circuit of 0.63 0.116 0.102 1.26 0.361 0.644
RO/RH(CPE1)/RL(CPE2) on Zview software. For the equivalent 1.41 0.0788 0.047 0.605 0.418 1.366
4 0.100 0.66 1.616 0.237 1.005
circuit, RO is the ohmic resistance of the device, including the

Please cite this article in press as: Wang B, et al., Advance fuel cells using Al2O3-nNaAlO2 composite as ion-conducting membrane,
International Journal of Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2018.04.149
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 8 ) 1 e9
value, this may be due to its optimal ability of charge migra-
tion. RL initially increased from 0.264 to 0.418 U cm2 as the
NaAlO2 content increase, further improving the NaAlO2 con-
tent reduced the RL to 0.237 U cm2. The sum of RH and RL is the
electrode polarization resistance (RP) [49], which corresponds
to the basic electrode reaction process. The fitted value of Rp
was 0.338, 0.463, 0.465 and 0.897 U cm2 at 575
C for the four
cells, respectively. These are significantly lower than that of
the reported LSCF/GDC counterpart, indicating Ni-NCAL
electrode has excellent catalysis activity, which contributed
to the superior power output of the assembled fuel cell.
Conclusion
Na2CO3 and Al2O3 mixture was calcined at 1100
C for 2 h, XRD
pattern revealed the product was salt-oxide Al2O3eNaAlO2
composite. Such composite was successfully applied as ion-
conducting membrane in advanced fuel cell, decent power
density of 789 mW/cm2 and high OCV of 1.13 V was obtained
at 575
C. EIS results disclosed the Al2O3eNaAlO2 composite
possessed expectedly high ionic conductivity, a highest ionic
conductivity of 0.121 S/cm was achieved for the Al2O3-
1.41NaAlO2 composite at 575
C, the high conductivity of
Al2O3-1.41NaAlO2 composite and the good catalysis activity of
NCAL electrode contributed to the promising performance of
assembled fuel cell.
Acknowledgment
The National Natural Science Foundation of China (NSFC,
No.51502084) would be sincerely appreciated for the financial
support.
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